Form and Function: An Organic Chemistry Module.

ERIC Educational Resources Information Center

Jarvis, Bruce; Mazzocchi, Paul

This book is one in the series of Interdisciplinary Approaches to Chemistry (IAC) designed to help students discover that chemistry is a lively science and actively used to pursue solutions to the important problems of today. It is expected for students to see how chemistry takes place continuously all around and to readily understand the daily…

Ascorbic Acid as a Standard for Iodometric Titrations. An Analytical Experiment for General Chemistry

NASA Astrophysics Data System (ADS)

Silva, Cesar R.; Simoni, Jose A.; Collins, Carol H.; Volpe, Pedro L. O.

1999-10-01

Ascorbic acid is suggested as the weighable compound for the standardization of iodine solutions in an analytical experiment in general chemistry. The experiment involves an iodometric titration in which iodine reacts with ascorbic acid, oxidizing it to dehydroascorbic acid. The redox titration endpoint is determined by the first iodine excess that is complexed with starch, giving a deep blue-violet color. The results of the titration of iodine solution using ascorbic acid as a calibration standard were compared with the results acquired by the classic method using a standardized solution of sodium thiosulfate. The standardization of the iodine solution using ascorbic acid was accurate and precise, with the advantages of saving time and avoiding mistakes due to solution preparation. The colorless ascorbic acid solution gives a very clear and sharp titration end point with starch. It was shown by thermogravimetric analysis that ascorbic acid can be dried at 393 K for 2 h without decomposition. This experiment allows general chemistry students to perform an iodometric titration during a single laboratory period, determining with precision the content of vitamin C in pharmaceutical formulations.

Flame Emission Spectrometry in General Chemistry Labs: Solubility Product (K[subscript sp]) of Potassium Hydrogen Phthalate

ERIC Educational Resources Information Center

Nyasulu, Frazier W.; Cusworth, William, III; Lindquist, David; Mackin, John

2007-01-01

In this general chemistry laboratory, flame emission spectrometry is used to determine the potassium ion concentration in saturated solutions of potassium hydrogen phthalate (KHP) in the 0-65 [degree]C temperature range. From these data the solubility products (K[subscript sp]), the Gibbs free energies of solution ([Delta][subscript…

A Study of First-Year Chemistry Students' Understanding of Solution Concentration at the Tertiary Level

ERIC Educational Resources Information Center

de Berg, Kevin

2012-01-01

This paper reports on students' understanding of sugar concentration in aqueous solutions presented in two different modes: a visual submicroscopic mode for particles and a verbal mode referring to macroscopic amounts of sugar. One hundred and forty-five tertiary college students studying some form of first-year chemistry participated in the…

Enhancing Pre-Service Elementary Teachers' Conceptual Understanding of Solution Chemistry with Conceptual Change Text

ERIC Educational Resources Information Center

Calik, Muammer; Ayas, Alipasa; Coll, Richard Kevin

2007-01-01

This paper reports on the use of a constructivist-based pedagogy to enhance understanding of some features of solution chemistry. Pre-service science teacher trainees' prior knowledge about the dissolution of salts and sugar in water were elicited by the use of a simple diagnostic tool. The test revealed widespread alternative conceptions. These…

Investigating the Effectiveness of Teaching Methods Based on a Four-Step Constructivist Strategy

NASA Astrophysics Data System (ADS)

Çalik, Muammer; Ayas, Alipaşa; Coll, Richard K.

2010-02-01

This paper reports on an investigation of the effectiveness an intervention using several different methods for teaching solution chemistry. The teaching strategy comprised a four-step approach derived from a constructivist view of learning. A sample consisting of 44 students (18 boys and 26 girls) was selected purposively from two different Grade 9 classes in the city of Trabzon, Turkey. Data collection employed a purpose-designed `solution chemistry concept test', consisting of 17 items, with the quantitative data from the survey supported by qualitative interview data. The findings suggest that using different methods embedded within the four-step constructivist-based teaching strategy enables students to refute some alternative conceptions, but does not completely eliminate student alternative conceptions for solution chemistry.

The Heart of Matter: A Nuclear Chemistry Module.

ERIC Educational Resources Information Center

Viola, Vic

This book is one in a series of Interdisciplinary Approaches to Chemistry (IAC) designed to help students discover that chemistry is a lively science and actively used to pursue solutions to the important problems of today. It is expected for students to see how chemistry takes place continuously all around and to readily understand the daily…

Computations of ideal and real gas high altitude plume flows

NASA Technical Reports Server (NTRS)

Feiereisen, William J.; Venkatapathy, Ethiraj

1988-01-01

In the present work, complete flow fields around generic space vehicles in supersonic and hypersonic flight regimes are studied numerically. Numerical simulation is performed with a flux-split, time asymptotic viscous flow solver that incorporates a generalized equilibrium chemistry model. Solutions to generic problems at various altitude and flight conditions show the complexity of the flow, the equilibrium chemical dissociation and its effect on the overall flow field. Viscous ideal gas solutions are compared against equilibrium gas solutions to illustrate the effect of equilibrium chemistry. Improved solution accuracy is achieved through adaptive grid refinement.

PROCEEDINGS OF THE PROTACTINIUM CHEMISTRY SYMPOSIUM, GATLINBURG, TENNESSEE, APRIL 25-26, 1963

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

1963-04-26

Eleven papers are presented on the chemistry of protactinium. Most of the emphasis is on solvent extraction and solution chemistry. Separate abstracts were prepared for ten of the papers; the remaining paper was previously abstracted in NSA. (D.L.C.)

Pretreatment of lignocellulosic biomass using Fenton chemistry

USDA-ARS?s Scientific Manuscript database

Pretreatment is a necessary step in “biomass to biofuel conversion” due to the recalcitrant nature of lignocellulosic biomass. White-rot fungi utilize peroxidases and hydrogen peroxide (in vivo Fenton chemistry) to degrade lignin. In an attempt to mimic this process, solution phase Fenton chemistry ...

GROUNDWATER MASS TRANSPORT AND EQUILIBRIUM CHEMISTRY MODEL FOR MULTICOMPONENT SYSTEMS

EPA Science Inventory

A mass transport model, TRANQL, for a multicomponent solution system has been developed. The equilibrium interaction chemistry is posed independently of the mass transport equations which leads to a set of algebraic equations for the chemistry coupled to a set of differential equ...

Transport of E. coli D21g with runoff water under different solution chemistry conditions and surface slopes

USDA-ARS?s Scientific Manuscript database

Tracer and indicator microbe runoff experiments were conducted to investigate the influence of solution chemistry on the transport, retention, and release of Escherichia coli D21g. Experiments were conducted in a chamber (2.25 m long, 0.15 m wide, and 0.16 m high) packed with ultrapure quartz sand (...

Challenges Faced by Pre-Service Chemistry Teachers Teaching in a Laboratory and Their Solution Proposals

ERIC Educational Resources Information Center

Yalcin-Celik, Ayse; Kadayifci, Hakki; Uner, Sinem; Turan-Oluk, Nurcan

2017-01-01

This study examines the challenges faced by pre-service chemistry teachers teaching in a laboratory and their proposed solutions to these challenges. The study was conducted in a 13-week-long methodology course. Written statements from participants and observations from researchers were used as data sources. From these data, it was found that the…

Role of Precursor-Conversion Chemistry in the Crystal-Phase Control of Catalytically Grown Colloidal Semiconductor Quantum Wires.

PubMed

Wang, Fudong; Buhro, William E

2017-12-26

Crystal-phase control is one of the most challenging problems in nanowire growth. We demonstrate that, in the solution-phase catalyzed growth of colloidal cadmium telluride (CdTe) quantum wires (QWs), the crystal phase can be controlled by manipulating the reaction chemistry of the Cd precursors and tri-n-octylphosphine telluride (TOPTe) to favor the production of either a CdTe solute or Te, which consequently determines the composition and (liquid or solid) state of the Bi x Cd y Te z catalyst nanoparticles. Growth of single-phase (e.g., wurtzite) QWs is achieved only from solid catalysts (y ≪ z) that enable the solution-solid-solid growth of the QWs, whereas the liquid catalysts (y ≈ z) fulfill the solution-liquid-solid growth of the polytypic QWs. Factors that affect the precursor-conversion chemistry are systematically accounted for, which are correlated with a kinetic study of the composition and state of the catalyst nanoparticles to understand the mechanism. This work reveals the role of the precursor-reaction chemistry in the crystal-phase control of catalytically grown colloidal QWs, opening the possibility of growing phase-pure QWs of other compositions.

Chemistry in Microfluidic Channels

ERIC Educational Resources Information Center

Chia, Matthew C.; Sweeney, Christina M.; Odom, Teri W.

2011-01-01

General chemistry introduces principles such as acid-base chemistry, mixing, and precipitation that are usually demonstrated in bulk solutions. In this laboratory experiment, we describe how chemical reactions can be performed in a microfluidic channel to show advanced concepts such as laminar fluid flow and controlled precipitation. Three sets of…

Using Games To Teach Chemistry: An Annotated Bibliography.

ERIC Educational Resources Information Center

Russell, Jeanne V.

1999-01-01

Lists 67 published or marketed chemistry games organized under the following categories: (1) general knowledge; (2) elements and atomic structure; (3) nomenclature, formulas, and equation writing; (4) chemical reactions; (5) solutions and solubilities; (6) organic chemistry, and (8) miscellaneous subjects. Includes a brief description of each…

An Analysis of 16-17-Year-Old Students' Understanding of Solution Chemistry Concepts Using a Two-Tier Diagnostic Instrument

ERIC Educational Resources Information Center

Adadan, Emine; Savasci, Funda

2012-01-01

This study focused on the development of a two-tier multiple-choice diagnostic instrument, which was designed and then progressively modified, and implemented to assess students' understanding of solution chemistry concepts. The results of the study are derived from the responses of 756 Grade 11 students (age 16-17) from 14 different high schools…

Effects of simulated acid rain on soil and soil solution chemistry in a monsoon evergreen broad-leaved forest in southern China.

PubMed

Qiu, Qingyan; Wu, Jianping; Liang, Guohua; Liu, Juxiu; Chu, Guowei; Zhou, Guoyi; Zhang, Deqiang

2015-05-01

Acid rain is an environmental problem of increasing concern in China. In this study, a laboratory leaching column experiment with acid forest soil was set up to investigate the responses of soil and soil solution chemistry to simulated acid rain (SAR). Five pH levels of SAR were set: 2.5, 3.0, 3.5, 4.0, and 4.5 (as a control, CK). The results showed that soil acidification would occur when the pH of SAR was ≤3.5. The concentrations of NO₃(-)and Ca(2+) in the soil increased significantly when the pH of SAR fell 3.5. The concentration of SO₄(2-) in the soil increased significantly when the pH of SAR was <4.0. The effects of SAR on soil solution chemistry became increasingly apparent as the experiment proceeded (except for Na(+) and dissolved organic carbon (DOC)). The net exports of NO₃(-), SO₄(2-), Mg(2+), and Ca(2+) increased about 42-86% under pH 2.5 treatment as compared to CK. The Ca(2+) was sensitive to SAR, and the soil could release Ca(2+) through mineral weathering to mitigate soil acidification. The concentration of exchangeable Al(3+) in the soil increased with increasing the acidity of SAR. The releases of soluble Al and Fe were SAR pH dependent, and their net exports under pH 2.5 treatment were 19.6 and 5.5 times, respectively, higher than that under CK. The net export of DOC was reduced by 12-29% under SAR treatments as compared to CK. Our results indicate the chemical constituents in the soil are more sensitive to SAR than those in the soil solution, and the effects of SAR on soil solution chemistry depend not only on the intensity of SAR but also on the duration of SAR addition. The soil and soil solution chemistry in this region may not be affected by current precipitation (pH≈4.5) in short term, but the soil and soil leachate chemistry may change dramatically if the pH of precipitation were below 3.5 and 3.0, respectively.

Proportional Reasoning in the Learning of Chemistry: Levels of Complexity

ERIC Educational Resources Information Center

Ramful, Ajay; Narod, Fawzia Bibi

2014-01-01

This interdisciplinary study sketches the ways in which proportional reasoning is involved in the solution of chemistry problems, more specifically, problems involving quantities in chemical reactions (commonly referred to as stoichiometry problems). By building on the expertise of both mathematics and chemistry education research, the present…

The Synthesis of Copper(II) Carboxylates Revisited

ERIC Educational Resources Information Center

Kushner, Kevin; Spangler, Robert E.; Salazar, Ralph A., Jr.; Lagowski, J. J.

2006-01-01

An electrochemical synthesis of copper(II) carboxylates has been developed and used in the general chemistry laboratory course for chemistry majors. This synthesis, using nonaqueous solutions, supplements the strategy of providing experiences in synthetic chemistry described by Yoder et al. ("J. Chem. Educ." 1995, 72, 267). (Contains 1 table.)

21 CFR 862.1540 - Osmolality test system.

Code of Federal Regulations, 2011 CFR

2011-04-01

...) MEDICAL DEVICES CLINICAL CHEMISTRY AND CLINICAL TOXICOLOGY DEVICES Clinical Chemistry Test Systems § 862... measure ionic and nonionic solute concentration in body fluids, such as serum and urine. Osmolality...

21 CFR 862.1540 - Osmolality test system.

Code of Federal Regulations, 2012 CFR

2012-04-01

...) MEDICAL DEVICES CLINICAL CHEMISTRY AND CLINICAL TOXICOLOGY DEVICES Clinical Chemistry Test Systems § 862... measure ionic and nonionic solute concentration in body fluids, such as serum and urine. Osmolality...

21 CFR 862.1540 - Osmolality test system.

Code of Federal Regulations, 2013 CFR

2013-04-01

...) MEDICAL DEVICES CLINICAL CHEMISTRY AND CLINICAL TOXICOLOGY DEVICES Clinical Chemistry Test Systems § 862... measure ionic and nonionic solute concentration in body fluids, such as serum and urine. Osmolality...

21 CFR 862.1540 - Osmolality test system.

Code of Federal Regulations, 2010 CFR

2010-04-01

...) MEDICAL DEVICES CLINICAL CHEMISTRY AND CLINICAL TOXICOLOGY DEVICES Clinical Chemistry Test Systems § 862... measure ionic and nonionic solute concentration in body fluids, such as serum and urine. Osmolality...

Pretreatment of lignocellulosic biomass using Fenton chemistry.

PubMed

Kato, Dawn M; Elía, Noelia; Flythe, Michael; Lynn, Bert C

2014-06-01

In an attempt to mimic white-rot fungi lignin degradation via in vivo Fenton chemistry, solution phase Fenton chemistry (10 g biomass, 176 mmol hydrogen peroxide and 1.25 mmol Fe(2+) in 200 mL of water) was applied to four different biomass feedstocks. An enzymatic saccharification of Fenton pretreated biomass showed an average 212% increase relative to untreated control across all four feedstocks (P<0.05, statistically significant). A microbial fermentation of the same Fenton pretreated biomass showed a threefold increase in gas production upon a sequential co-culture with Clostridium thermocellum and Clostridium beijerinckii. These results demonstrate the use of solution phase Fenton chemistry as a viable pretreatment method to make cellulose more bioavailable for microbial biofuel conversion. Copyright © 2014 Elsevier Ltd. All rights reserved.

Prebiotic chemistry in eutectic solutions at the water-ice matrix.

PubMed

Menor-Salván, César; Marín-Yaseli, Margarita R

2012-08-21

A crystalline ice matrix at subzero temperatures can maintain a liquid phase where organic solutes and salts concentrate to form eutectic solutions. This concentration effect converts the confined reactant solutions in the ice matrix, sometimes making condensation and polymerisation reactions occur more favourably. These reactions occur at significantly high rates from a prebiotic chemistry standpoint, and the labile products can be protected from degradation. The experimental study of the synthesis of nitrogen heterocycles at the ice-water system showed the efficiency of this scenario and could explain the origin of nucleobases in the inner Solar System bodies, including meteorites and extra-terrestrial ices, and on the early Earth. The same conditions can also favour the condensation of monomers to form ribonucleic acid and peptides. Together with the synthesis of these monomers, the ice world (i.e., the chemical evolution in the range between the freezing point of water and the limit of stability of liquid brines, 273 to 210 K) is an under-explored experimental model in prebiotic chemistry.

College Students Solving Chemistry Problems: A Theoretical Model of Expertise

ERIC Educational Resources Information Center

Taasoobshirazi, Gita; Glynn, Shawn M.

2009-01-01

A model of expertise in chemistry problem solving was tested on undergraduate science majors enrolled in a chemistry course. The model was based on Anderson's "Adaptive Control of Thought-Rational" (ACT-R) theory. The model shows how conceptualization, self-efficacy, and strategy interact and contribute to the successful solution of quantitative,…

Dynamic Vertical Profiles of Peat Porewater Chemistry in a Northern Peatland

DOE Office of Scientific and Technical Information (OSTI.GOV)

Griffiths, Natalie A.; Sebestyen, Stephen D.

We measured pH, cations, nutrients, and total organic carbon (TOC) over 3 years to examine weekly to monthly variability in porewater chemistry depth profiles (0–3.0 m) in an ombrotrophic bog in Minnesota, USA. We also compared temporal variation at one location to spatial variation in depth profiles at 16 locations across the bog. Most solutes exhibited large gradients with depth. pH increased by two units and calcium concentrations increased over 20 fold with depth, and may reflect peatland development from minerotrophic to ombrotrophic conditions. Ammonium concentrations increased almost 20 fold and TOC concentrations decreased by half with depth, and thesemore » patterns likely reflect mineralization of peat or decomposition of TOC. There was also considerable temporal variation in the porewater chemistry depth profiles. Ammonium, soluble reactive phosphorus, and potassium showed greater temporal variation in near-surface porewater, while pH, calcium, and TOC varied more at depth. This variation demonstrates that deep peat porewater chemistry is not static. Lastly, temporal variation in solute chemistry depth profiles was greater than spatial variation in several instances, especially in shallow porewaters. In conclusion, characterizing both temporal and spatial variability is necessary to ensure representative sampling in peatlands, especially when calculating solute pools and fluxes and parameterizing process-based models.« less

Dynamic Vertical Profiles of Peat Porewater Chemistry in a Northern Peatland

DOE PAGES

Griffiths, Natalie A.; Sebestyen, Stephen D.

2016-10-14

We measured pH, cations, nutrients, and total organic carbon (TOC) over 3 years to examine weekly to monthly variability in porewater chemistry depth profiles (0–3.0 m) in an ombrotrophic bog in Minnesota, USA. We also compared temporal variation at one location to spatial variation in depth profiles at 16 locations across the bog. Most solutes exhibited large gradients with depth. pH increased by two units and calcium concentrations increased over 20 fold with depth, and may reflect peatland development from minerotrophic to ombrotrophic conditions. Ammonium concentrations increased almost 20 fold and TOC concentrations decreased by half with depth, and thesemore » patterns likely reflect mineralization of peat or decomposition of TOC. There was also considerable temporal variation in the porewater chemistry depth profiles. Ammonium, soluble reactive phosphorus, and potassium showed greater temporal variation in near-surface porewater, while pH, calcium, and TOC varied more at depth. This variation demonstrates that deep peat porewater chemistry is not static. Lastly, temporal variation in solute chemistry depth profiles was greater than spatial variation in several instances, especially in shallow porewaters. In conclusion, characterizing both temporal and spatial variability is necessary to ensure representative sampling in peatlands, especially when calculating solute pools and fluxes and parameterizing process-based models.« less

A comparison of methods for deriving solute flux rates using long-term data from streams in the mirror lake watershed

USGS Publications Warehouse

Bukaveckas, P.A.; Likens, G.E.; Winter, T.C.; Buso, D.C.

1998-01-01

Calculation of chemical flux rates for streams requires integration of continuous measurements of discharge with discrete measurements of solute concentrations. We compared two commonly used methods for interpolating chemistry data (time-averaging and flow-weighting) to determine whether discrepancies between the two methods were large relative to other sources of error in estimating flux rates. Flux rates of dissolved Si and SO42- were calculated from 10 years of data (1981-1990) for the NW inlet and Outlet of Mirror Lake and for a 40-day period (March 22 to April 30, 1993) during which we augmented our routine (weekly) chemical monitoring with collection of daily samples. The time-averaging method yielded higher estimates of solute flux during high-flow periods if no chemistry samples were collected corresponding to peak discharge. Concentration-discharge relationships should be used to interpolate stream chemistry during changing flow conditions if chemical changes are large. Caution should be used in choosing the appropriate time-scale over which data are pooled to derive the concentration-discharge regressions because the model parameters (slope and intercept) were found to be sensitive to seasonal and inter-annual variation. Both methods approximated solute flux to within 2-10% for a range of solutes that were monitored during the intensive sampling period. Our results suggest that errors arising from interpolation of stream chemistry data are small compared with other sources of error in developing watershed mass balances.

Monte Carlo simulation of a near-continuum shock-shock interaction problem

NASA Technical Reports Server (NTRS)

Carlson, Ann B.; Wilmoth, Richard G.

1992-01-01

A complex shock interaction is calculated with direct simulation Monte Carlo (DSMC). The calculation is performed for the near-continuum flow produced when an incident shock impinges on the bow shock of a 0.1 in. radius cowl lip for freestream conditions of approximately Mach 15 and 35 km altitude. Solutions are presented both for a full finite-rate chemistry calculation and for a case with chemical reactions suppressed. In each case, both the undisturbed flow about the cowl lip and the full shock interaction flowfields are calculated. Good agreement has been obtained between the no-chemistry simulation of the undisturbed flow and a perfect gas solution obtained with the viscous shock-layer method. Large differences in calculated surface properties when different chemical models are used demonstrate the necessity of adequately representing the chemistry when making surface property predictions. Preliminary grid refinement studies make it possible to estimate the accuracy of the solutions.

An Investigation of the Effects of Relevant Samples and a Comparison of Verification versus Discovery Based Lab Design

ERIC Educational Resources Information Center

Rieben, James C., Jr.

2010-01-01

This study focuses on the effects of relevance and lab design on student learning within the chemistry laboratory environment. A general chemistry conductivity of solutions experiment and an upper level organic chemistry cellulose regeneration experiment were employed. In the conductivity experiment, the two main variables studied were the effect…

An Introduction to the Fundamentals of Chemistry for the Marine Engineer - An Audio-Tutorial Correspondence Course (CH-1C).

ERIC Educational Resources Information Center

Schlenker, Richard M.

This document provides a study guide for a three-credit-hour fundamentals of chemistry course for marine engineer majors. The course is composed of 17 minicourses including: chemical reactions, atomic theory, solutions, corrosion, organic chemistry, water pollution, metric system, and remedial mathematics skills. Course grading, objectives,…

Analysis of Copper-Bearing Rocks and Minerals for Their Metal Content Using Visible Spectroscopy: A First Year Chemistry Laboratory Exploration

ERIC Educational Resources Information Center

Bopegedera, A. M. R. P.

2016-01-01

General chemistry and introductory chemistry students were presented with a laboratory exploration for the determination of the mass percent of copper in rock and mineral samples. They worked independently in the laboratory, which involved multiple lab (pipetting, preparing standard solutions by quantitative dilution, recording visible spectra…

Evaluating the effects of variable water chemistry on bacterial transport during infiltration.

PubMed

Zhang, Haibo; Nordin, Nahjan Amer; Olson, Mira S

2013-07-01

Bacterial infiltration through the subsurface has been studied experimentally under different conditions of interest and is dependent on a variety of physical, chemical and biological factors. However, most bacterial transport studies fail to adequately represent the complex processes occurring in natural systems. Bacteria are frequently detected in stormwater runoff, and may present risk of microbial contamination during stormwater recharge into groundwater. Mixing of stormwater runoff with groundwater during infiltration results in changes in local solution chemistry, which may lead to changes in both bacterial and collector surface properties and subsequent bacterial attachment rates. This study focuses on quantifying changes in bacterial transport behavior under variable solution chemistry, and on comparing the influences of chemical variability and physical variability on bacterial attachment rates. Bacterial attachment rate at the soil-water interface was predicted analytically using a combined rate equation, which varies temporally and spatially with respect to changes in solution chemistry. Two-phase Monte Carlo analysis was conducted and an overall input-output correlation coefficient was calculated to quantitatively describe the importance of physiochemical variation on the estimates of attachment rate. Among physical variables, soil particle size has the highest correlation coefficient, followed by porosity of the soil media, bacterial size and flow velocity. Among chemical variables, ionic strength has the highest correlation coefficient. A semi-reactive microbial transport model was developed within HP1 (HYDRUS1D-PHREEQC) and applied to column transport experiments with constant and variable solution chemistries. Bacterial attachment rates varied from 9.10×10(-3)min(-1) to 3.71×10(-3)min(-1) due to mixing of synthetic stormwater (SSW) with artificial groundwater (AGW), while bacterial attachment remained constant at 9.10×10(-3)min(-1) in a constant solution chemistry (AGW only). The model matched observed bacterial breakthrough curves well. Although limitations exist in the application of a semi-reactive microbial transport model, this method represents one step towards a more realistic model of bacterial transport in complex microbial-water-soil systems. Copyright © 2013 Elsevier B.V. All rights reserved.

Chemistry Division. Quarterly progress report for period ending June 30, 1949

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1949-09-14

Progress reports are presented for the following tasks: (1) nuclear and chemical properties of heavy elements (solution chemistry, phase rule studies); (2) nuclear and chemical properties of elements in the fission product region; (3) general nuclear chemistry; (4) radio-organic chemistry; (5) chemistry of separations processes; (6) physical chemistry and chemical physics; (7) radiation chemistry; (8) physical measurements and instrumentation; and (9) analytical chemistry. The program of the chemistry division is divided into two efforts of approximately equal weight with respect to number of personnel, chemical research, and analytical service for the Laboratory. The various research problems fall into the followingmore » classifications: (1) chemical separation processes for isolation and recovery of fissionable material, production of radioisotopes, and military applications; (2) reactor development; and (3) fundamental research.« less

Pierre-Joseph Macquer: Chemistry in the French Enlightenment.

PubMed

Lehman, Christine

2014-01-01

Despite recent studies of chemistry courses and of academic research at the beginning of the eighteenth century, the perception of chemistry in the French Enlightenment has often been overshadowed by Lavoisier's works. This article proposes three specific case studies selected from Pierre Joseph Macquer's (1718-84) rich career to show the continuous evolution of chemistry throughout the century: medicinal chemistry through the application of the Comte de La Garaye's metallic salt solutions, the emergence of industrial chemistry through a few of Macquer's evaluations at the Bureau du Commerce, and finally communal academic research through the experiments on diamonds using Tschirnhaus's lens. These examples attempt to illustrate the innovative, creative, dynamic, multicultural, and multifaceted chemistry of the Enlightenment.

Multi-Scale Modeling of the Gamma Radiolysis of Nitrate Solutions.

PubMed

Horne, Gregory P; Donoclift, Thomas A; Sims, Howard E; Orr, Robin M; Pimblott, Simon M

2016-11-17

A multiscale modeling approach has been developed for the extended time scale long-term radiolysis of aqueous systems. The approach uses a combination of stochastic track structure and track chemistry as well as deterministic homogeneous chemistry techniques and involves four key stages: radiation track structure simulation, the subsequent physicochemical processes, nonhomogeneous diffusion-reaction kinetic evolution, and homogeneous bulk chemistry modeling. The first three components model the physical and chemical evolution of an isolated radiation chemical track and provide radiolysis yields, within the extremely low dose isolated track paradigm, as the input parameters for a bulk deterministic chemistry model. This approach to radiation chemical modeling has been tested by comparison with the experimentally observed yield of nitrite from the gamma radiolysis of sodium nitrate solutions. This is a complex radiation chemical system which is strongly dependent on secondary reaction processes. The concentration of nitrite is not just dependent upon the evolution of radiation track chemistry and the scavenging of the hydrated electron and its precursors but also on the subsequent reactions of the products of these scavenging reactions with other water radiolysis products. Without the inclusion of intratrack chemistry, the deterministic component of the multiscale model is unable to correctly predict experimental data, highlighting the importance of intratrack radiation chemistry in the chemical evolution of the irradiated system.

A Study of the Liquid-Liquid Partitioning Process Using Reverse-Phase Liquid Chromatography: An Undergraduate Analytical Chemistry Experiment.

ERIC Educational Resources Information Center

Lochmuller, C. H.; And Others

1980-01-01

Presents an undergraduate analytical chemistry experiment that promotes an interpretation of the molecular aspects of solute partitioning, enhancing student understanding of separation science and liquid chromatography. (CS)

Electrolyte Solutions and Specific Ion Effects on Interfaces

ERIC Educational Resources Information Center

Friedman, Ran

2013-01-01

Introductory general and physical chemistry courses often deal with colligative properties of solutions and do not discuss nonideal solutions in detail. Yet, a growing body of evidence reveals that even at physiological concentrations electrolyte solutions cannot be treated as ideal when a charged or partially charged solute (such as a protein) is…

Techniques To Enhance Instructors' Teaching Effectiveness with Chemistry Students Who Are Blind or Visually Impaired

NASA Astrophysics Data System (ADS)

Supalo, Cary

2005-10-01

This paper describes techniques developed as solutions to problems encountered while teaching blind or visually impaired students in chemistry courses at high school and postsecondary levels. Establishing and maintaining a sound student instructor relationship is critical to the success and implementation of a plan of action for blind or visually impaired students enrolled in chemistry courses.

Survey of application of radiation to preparative chemistry

NASA Technical Reports Server (NTRS)

Philipp, W. H.

1973-01-01

The use of radiation for preparative chemistry in liquid solutions is investigated. General principles are presented and preparations involving reduction, oxidation, polymerization, and decomposition are given. The use of various solvents, water, other inorganic liquids and organic liquids for this purpose is discussed. Finally, a commentary is made on some specific applications where radiation chemistry as a preparative technique may be useful.

Introduction to Computational Chemistry: Teaching Hu¨ckel Molecular Orbital Theory Using an Excel Workbook for Matrix Diagonalization

ERIC Educational Resources Information Center

Litofsky, Joshua; Viswanathan, Rama

2015-01-01

Matrix diagonalization, the key technique at the heart of modern computational chemistry for the numerical solution of the Schrödinger equation, can be easily introduced in the physical chemistry curriculum in a pedagogical context using simple Hückel molecular orbital theory for p bonding in molecules. We present details and results of…

Independent Learning Project for Advanced Chemistry (ILPAC). Teachers' and Technicians' Notes for First Year Units.

ERIC Educational Resources Information Center

Inner London Education Authority (England).

The Independent Learning Project for Advanced Chemistry (ILPAC) has produced units of study for students in A-level chemistry. Students completing ILPAC units assume a greater responsibility for their own learning and can work, to some extent, at their own pace. By providing guidance, and detailed solutions to exercises in the units, supported by…

Computational chemistry

NASA Technical Reports Server (NTRS)

Arnold, J. O.

1987-01-01

With the advent of supercomputers, modern computational chemistry algorithms and codes, a powerful tool was created to help fill NASA's continuing need for information on the properties of matter in hostile or unusual environments. Computational resources provided under the National Aerodynamics Simulator (NAS) program were a cornerstone for recent advancements in this field. Properties of gases, materials, and their interactions can be determined from solutions of the governing equations. In the case of gases, for example, radiative transition probabilites per particle, bond-dissociation energies, and rates of simple chemical reactions can be determined computationally as reliably as from experiment. The data are proving to be quite valuable in providing inputs to real-gas flow simulation codes used to compute aerothermodynamic loads on NASA's aeroassist orbital transfer vehicles and a host of problems related to the National Aerospace Plane Program. Although more approximate, similar solutions can be obtained for ensembles of atoms simulating small particles of materials with and without the presence of gases. Computational chemistry has application in studying catalysis, properties of polymers, all of interest to various NASA missions, including those previously mentioned. In addition to discussing these applications of computational chemistry within NASA, the governing equations and the need for supercomputers for their solution is outlined.

Hydrated Cations in the General Chemistry Course.

ERIC Educational Resources Information Center

Kauffman, George B.; Baxter, John F., Jr.

1981-01-01

Presents selected information regarding the descriptive chemistry of the common metal ions and their compounds, including the concepts of process of solution, polar molecules, ionic size and charge, complex ions, coordination number, and the Bronsted-Lowry acid-base theory. (CS)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lawrence, G.B.; Fernandez, I.J.; Goltz, S.M.

To provide information needed to assess the current and future status of spruce-fir forests in Maine, the Howland Integrated Forest Study (HIFS) was initiated in 1987 as part of the USDA Forest Service Forest Response Program, in conjunction with the establishment of a Mountain Cloud Chemistry Program (MCCP) monitoring site. Through this project, bulk and wet-only precipitation, dry deposition, throughfall and soil solution chemistry has been determined. This paper will focus on soil solution collected between May, 1988 and bulk precipitation collected from June through November, 1988.

Using Games To Teach Chemistry: An Annotated Bibliography

NASA Astrophysics Data System (ADS)

Russell, Jeanne V.

1999-04-01

A list of published or marketed games based on a chemistry motif is presented. Each game is listed according to its level, subject matter, and title. A bibliographic notation and a short description are given for each game. For Introductory/High School/General Chemistry, 45 games are listed under the subjects General Knowledge; Elements & Atomic Structure (not Symbols); Nomenclature, Formulas, & Equation Writing; Chemical Reactions: Solutions & Solubilities; and Other Subjects. Seventeen games are listed under Organic Chemistry and 4 games under Other Chemistry Games. Computer games designed for outdated computers (PDP-11, TRS-80, and Apple II) are not included.

Microfluidics for High School Chemistry Students.

PubMed

Hemling, Melissa; Crooks, John A; Oliver, Piercen M; Brenner, Katie; Gilbertson, Jennifer; Lisensky, George C; Weibel, Douglas B

2014-01-14

We present a laboratory experiment that introduces high school chemistry students to microfluidics while teaching fundamental properties of acid-base chemistry. The procedure enables students to create microfluidic systems using nonspecialized equipment that is available in high school classrooms and reagents that are safe, inexpensive, and commercially available. The experiment is designed to ignite creativity and confidence about experimental design in a high school chemistry class. This experiment requires a computer program (e.g., PowerPoint), Shrinky Dink film, a readily available silicone polymer, weak acids, bases, and a colorimetric pH indicator. Over the span of five 45-min class periods, teams of students design and prepare devices in which two different pH solutions mix in a predictable way to create five different pH solutions. Initial device designs are instructive but rarely optimal. During two additional half-class periods, students have the opportunity to use their initial observations to redesign their microfluidic systems to optimize the outcome. The experiment exposes students to cutting-edge science and the design process, and solidifies introductory chemistry concepts including laminar flow, neutralization of weak acids-bases, and polymers.

Microfluidics for High School Chemistry Students

PubMed Central

Hemling, Melissa; Crooks, John A.; Oliver, Piercen M.; Brenner, Katie; Gilbertson, Jennifer; Lisensky, George C.; Weibel, Douglas B.

2014-01-01

We present a laboratory experiment that introduces high school chemistry students to microfluidics while teaching fundamental properties of acid–base chemistry. The procedure enables students to create microfluidic systems using nonspecialized equipment that is available in high school classrooms and reagents that are safe, inexpensive, and commercially available. The experiment is designed to ignite creativity and confidence about experimental design in a high school chemistry class. This experiment requires a computer program (e.g., PowerPoint), Shrinky Dink film, a readily available silicone polymer, weak acids, bases, and a colorimetric pH indicator. Over the span of five 45-min class periods, teams of students design and prepare devices in which two different pH solutions mix in a predictable way to create five different pH solutions. Initial device designs are instructive but rarely optimal. During two additional half-class periods, students have the opportunity to use their initial observations to redesign their microfluidic systems to optimize the outcome. The experiment exposes students to cutting-edge science and the design process, and solidifies introductory chemistry concepts including laminar flow, neutralization of weak acids–bases, and polymers. PMID:25584013

JPRS Report, Science & Technology, USSR: Chemistry.

DTIC Science & Technology

1987-08-18

ZHURNAL PRIKLADNOY KHIMII, No 11, Nov 86). 64 Hydrothermal Chemistry of Gallium Alpha-orthophosphate in Orthophosphoric Acid (A. A, Adkhamov, B. S...precipitation from nitrate solutions with ammonium oxalate , heating to 400 deg and calcining at 800, 950 and 1100 deg for 4 hours. A high catalytic...12765/9835 CSO: 1841/215 UDC 548.54 HYDROTHERMAL CHEMISTRY OF GALLIUM ALPHA-ORTHOPHOSPHATE IN ORTHOPHOSPHORIC ACID Moscow DOKLADY AKADEMII NAUK

Understanding `green chemistry' and `sustainability': an example of problem-based learning (PBL)

NASA Astrophysics Data System (ADS)

Günter, Tuğçe; Akkuzu, Nalan; Alpat, Şenol

2017-10-01

Background: This study uses problem-based learning (PBL) to ensure that students comprehend the significance of green chemistry better by experiencing the stages of identifying the problem, developing hypotheses, and providing solutions within the problem-solving process.

Education in Environmental Chemistry: Setting the Agenda and Recommending Action

ERIC Educational Resources Information Center

Zoller, Uri

2005-01-01

The effective utilization of Education in Environmental Chemistry (EEC) in addressing global and societal environmental problems requires integration between educational, technical, financial, ethical and societal considerations. An interdisciplinary approach is fundamental to efforts to achieve long-term solutions.

Chemical evaluation of soil-solution in acid forest soils

USGS Publications Warehouse

Lawrence, G.B.; David, M.B.

1996-01-01

Soil-solution chemistry is commonly studied in forests through the use of soil lysimeters.This approach is impractical for regional survey studies, however, because lysimeter installation and operation is expensive and time consuming. To address these problems, a new technique was developed to compare soil-solution chemistry among red spruce stands in New York, Vermont, New Hampshire, Maine. Soil solutions were expelled by positive air pressure from soil that had been placed in a sealed cylinder. Before the air pressure was applied, a solution chemically similar to throughfall was added to the soil to bring it to approximate field capacity. After the solution sample was expelled, the soil was removed from the cylinder and chemically analyzed. The method was tested with homogenized Oa and Bs horizon soils collected from a red spruce stand in the Adirondack Mountains of New York, a red spruce stand in east-central Vermont, and a mixed hardwood stand in the Catskill Mountains of New York. Reproducibility, effects of varying the reaction time between adding throughfall and expelling soil solution (5-65 minutes) and effects of varying the chemical composition of added throughfall, were evaluated. In general, results showed that (i) the method was reproducible (coefficients of variation were generally < 15%), (ii) variations in the length of reaction-time did not affect expelled solution concentrations, and (iii) adding and expelling solution did not cause detectable changes in soil exchange chemistry. Concentrations of expelled solutions varied with the concentrations of added throughfall; the lower the CEC, the more sensitive expelled solution concentrations were to the chemical concentrations of added throughfall. Addition of a tracer (NaBr) showed that the expelled solution was a mixture of added solution and solution that preexisted in the soil. Comparisons of expelled solution concentrations with concentrations of soil solutions collected by zero-tension and tension lysimetry indicated that expelled solution concentrations were higher than those obtained with either type of lysimeter, although there was less difference with tension lysimeters than zero-tension lysimeters. The method used for collection of soil solution should be taken into consideration whenever soil solution data are being interpreted.

Solution chemistry of carbonate minerals and its effects on the flotation of hematite with sodium oleate

NASA Astrophysics Data System (ADS)

Li, Dong; Yin, Wan-zhong; Xue, Ji-wei; Yao, Jin; Fu, Ya-feng; Liu, Qi

2017-07-01

The effects of carbonate minerals (dolomite and siderite) on the flotation of hematite using sodium oleate as a collector were investigated through flotation tests, supplemented by dissolution measurements, solution chemistry calculations, zeta-potential measurements, Fourier transform infrared (FTIR) spectroscopic studies, and X-ray photoelectron spectroscopy (XPS) analyses. The results of flotation tests show that the presence of siderite or dolomite reduced the recovery of hematite and that the inhibiting effects of dolomite were stronger. Dissolution measurements, solution chemistry calculations, and flotation tests confirmed that both the cations (Ca2+ and Mg2+) and CO3 2- ions dissolved from dolomite depressed hematite flotation, whereas only the CO3 2- ions dissolved from siderite were responsible for hematite depression. The zeta-potential, FTIR spectroscopic, and XPS analyses indicated that Ca2+, Mg2+, and CO3 2- (HCO3 -) could adsorb onto the hematite surface, thereby hindering the adsorption of sodium oleate, which was the main reason for the inhibiting effects of carbonate minerals on hematite flotation.

Entertaining Chemistry--Two Colorful Reactions.

ERIC Educational Resources Information Center

Elsworth, John F.

2000-01-01

Describes two related color-change reactions that are relatively easy and safe to demonstrate. In the "Sunday School Reaction", a black and a white solution are mixed to form a white solution. In the "South Africa Reaction", a series of black, brown, red, and white solutions are mixed to form a clear, colorless solution. (WRM)

Mineral Type and Solution Chemistry Affect the Structure and Composition of Actively Growing Bacterial Communities as Revealed by Bromodeoxyuridine Immunocapture and 16S rRNA Pyrosequencing.

PubMed

Kelly, L C; Colin, Y; Turpault, M-P; Uroz, S

2016-08-01

Understanding how minerals affect bacterial communities and their in situ activities in relation to environmental conditions are central issues in soil microbial ecology, as minerals represent essential reservoirs of inorganic nutrients for the biosphere. To determine the impact of mineral type and solution chemistry on soil bacterial communities, we compared the diversity, composition, and functional abilities of a soil bacterial community incubated in presence/absence of different mineral types (apatite, biotite, obsidian). Microcosms were prepared containing different liquid culture media devoid of particular essential nutrients, the nutrients provided only in the introduced minerals and therefore only available to the microbial community through mineral dissolution by biotic and/or abiotic processes. By combining functional screening of bacterial isolates and community analysis by bromodeoxyuridine DNA immunocapture and 16S rRNA gene pyrosequencing, we demonstrated that bacterial communities were mainly impacted by the solution chemistry at the taxonomic level and by the mineral type at the functional level. Metabolically active bacterial communities varied with solution chemistry and mineral type. Burkholderia were significantly enriched in the obsidian treatment compared to the biotite treatment and were the most effective isolates at solubilizing phosphorous or mobilizing iron, in all the treatments. A detailed analysis revealed that the 16S rRNA gene sequences of the OTUs or isolated strains assigned as Burkholderia in our study showed high homology with effective mineral-weathering bacteria previously recovered from the same experimental site.

Imidazole as a pH Probe: An NMR Experiment for the General Chemistry Laboratory

ERIC Educational Resources Information Center

Hagan, William J., Jr.; Edie, Dennis L.; Cooley, Linda B.

2007-01-01

The analysis describes an NMR experiment for the general chemistry laboratory, which employs an unknown imidazole solution to measure the pH values. The described mechanism can also be used for measuring the acidity within the isolated cells.

Visualizing Chemistry: Investigations for Teachers.

ERIC Educational Resources Information Center

Ealy, Julie B.; Ealy, James L., Jr.

This book contains 101 investigations for chemistry classrooms. Topics include: (1) Physical Properties; (2) Reactions of Some Elements; (3) Reactions Involving Gases; (4) Energy Changes; (5) Solutions and Solubility; (6) Transition Metals and Complex Ions; (7) Kinetics and Equilibrium; (8) Acids and Bases; (9) Oxidation-Reduction; (10)…

Plastic Bags to Batteries: A Green Chemistry Solution

ScienceCinema

Pol, Vilas

2018-04-16

Plastic bags are the scourge of roadsides, parking lots and landfills. But chemistry comes to the rescue! At Argonne National Laboratory, Vilas Pol has found a way to not only recycle plastic bags--but make them into valuable batteries for cell phones and laptops.

Plastic Bags to Batteries: A Green Chemistry Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pol, Vilas

2010-01-01

Plastic bags are the scourge of roadsides, parking lots and landfills. But chemistry comes to the rescue! At Argonne National Laboratory, Vilas Pol has found a way to not only recycle plastic bags--but make them into valuable batteries for cell phones and laptops.

Effect of non-equilibrium flow chemistry and surface catalysis on surface heating to AFE

NASA Technical Reports Server (NTRS)

Stewart, David A.; Henline, William D.; Chen, Yih-Kanq

1991-01-01

The effect of nonequilibrium flow chemistry on the surface temperature distribution over the forebody heat shield on the Aeroassisted Flight Experiment (AFE) vehicle was investigated using a reacting boundary-layer code. Computations were performed by using boundary-layer-edge properties determined from global iterations between the boundary-layer code and flow field solutions from a viscous shock layer (VSL) and a full Navier-Stokes solution. Surface temperature distribution over the AFE heat shield was calculated for two flight conditions during a nominal AFE trajectory. This study indicates that the surface temperature distribution is sensitive to the nonequilibrium chemistry in the shock layer. Heating distributions over the AFE forebody calculated using nonequilibrium edge properties were similar to values calculated using the VSL program.

First-Principles pH Theory

NASA Astrophysics Data System (ADS)

Kim, Yong-Hyun; Zhang, S. B.

2006-03-01

Despite being one of the most important macroscopic measures and a long history even before the quantum mechanics, the concept of pH has rarely been mentioned in microscopic theories, nor being incorporated computationally into first-principles theory of aqueous solutions. Here, we formulate a theory for the pH dependence of solution formation energy by introducing the proton chemical potential as the microscopic counterpart of pH in atomistic solution models. Within the theory, the general acid-base chemistry can be cast in a simple pictorial representation. We adopt density-functional molecular dynamics to demonstrate the usefulness of the method by studying a number of solution systems including water, small solute molecules such as NH3 and HCOOH, and more complex amino acids with several functional groups. For pure water, we calculated the auto- ionization constant to be 13.2 with a 95 % accuracy. For other solutes, the calculated dissociation constants, i.e., the so- called pKa, are also in reasonable agreement with experiments. Our first-principles pH theory can be readily applied to broad solution chemistry problems such as redox reactions.

Aqueous Plasma Pharmacy: Preparation Methods, Chemistry, and Therapeutic Applications

PubMed Central

Joslin, Jessica M.; McCall, James R.; Bzdek, Justin P.; Johnson, Derek C.; Hybertson, Brooks M.

2017-01-01

Plasma pharmacy is a subset of the broader field of plasma medicine. Although not strictly defined, the term aqueous plasma pharmacy (APP) is used to refer to the generation and distribution of reactive plasma-generated species in an aqueous solution followed by subsequent administration for therapeutic benefits. APP attempts to harness the therapeutic effects of plasma-generated oxidant species within aqueous solution in various applications, such as disinfectant solutions, cell proliferation related to wound healing, and cancer treatment. The subsequent use of plasma-generated solutions in the APP approach facilitates the delivery of reactive plasma species to internal locations within the body. Although significant efforts in the field of plasma medicine have concentrated on employing direct plasma plume exposure to cells or tissues, here we focus specifically on plasma discharge in aqueous solution to render the solution biologically active for subsequent application. Methods of plasma discharge in solution are reviewed, along with aqueous plasma chemistry and the applications for APP. The future of the field also is discussed regarding necessary research efforts that will enable commercialization for clinical deployment. PMID:28428835

A Practical and Convenient Diffusion Apparatus: An Undergraduate Physical Chemistry Experiment.

ERIC Educational Resources Information Center

Clifford, Ben; Ochiai, E. I.

1980-01-01

Described is a diffusion apparatus to be used in an undergraduate physical chemistry laboratory experiment to determine the diffusion coefficients of aqueous solutions of sucrose and potassium dichromate. Included is the principle of the method, apparatus design and description, and experimental procedure. (Author/DS)

EPR Studies of Spin-Spin Exchange Processes: A Physical Chemistry Experiment.

ERIC Educational Resources Information Center

Eastman, Michael P.

1982-01-01

Theoretical background, experimental procedures, and analysis of experimental results are provided for an undergraduate physical chemistry experiment on electron paramagnetic resonance (EPR) linewidths. Source of line broadening observed in a spin-spin exchange process between radicals formed in aqueous solutions of potassium peroxylamine…

SOME ASPECTS OF THE CHEMISTRY OF POLYSULFIDE PULPING,

DTIC Science & Technology

Kraft pulping with the addition of polysulfide, i.e. polysulfide pulping, is one of the few methods available which can be used to increase the yield...and change the properties of kraft pulp. The chemistry of aqueous polysulfide solutions and the concurrent reactions occurring in polysulfide pulping

Life's Biological Chemistry: A Destiny or Destination Starting from Prebiotic Chemistry?

PubMed

Krishnamurthy, Ramanarayanan

2018-06-05

Research into understanding the origins -and evolution- of life has long been dominated by the concept of taking clues from extant biology and extrapolating its molecules and pathways backwards in time. This approach has also guided the search for solutions to the problem of how contemporary biomolecules would have arisen directly from prebiotic chemistry on early earth. However, the continuing difficulties in finding universally convincing solutions in connecting prebiotic chemistry to biological chemistry should give us pause, and prompt us to rethink this concept of treating extant life's chemical processes as the sole end goal and, therefore, focusing only -and implicitly- on the respective extant chemical building blocks. Rather, it may be worthwhile "to set aside the goal" and begin with what would have been plausible prebiotic reaction mixtures (which may have no obvious or direct connection to life's chemical building blocks and processes) - and allow their chemistries and interactions, under different geochemical constraints, to guide and illuminate as to what processes and systems can emerge. Such a conceptual approach gives rise to the prospect that chemistry of life-as-we-know-it is not the only result (not a "destiny"), but one that has emerged among many potential possibilities (a "destination"). This postulate, in turn, could impact the way we think about chemical signatures and criteria used in the search for alternative and extraterrestrial "life". As a bonus, we may discover the chemistries and pathways naturally that led to the emergence of life as we know it. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Connecting Biology and Organic Chemistry Introductory Laboratory Courses through a Collaborative Research Project

ERIC Educational Resources Information Center

Boltax, Ariana L.; Armanious, Stephanie; Kosinski-Collins, Melissa S.; Pontrello, Jason K.

2015-01-01

Modern research often requires collaboration of experts in fields, such as math, chemistry, biology, physics, and computer science to develop unique solutions to common problems. Traditional introductory undergraduate laboratory curricula in the sciences often do not emphasize connections possible between the various disciplines. We designed an…

Coloring a Superabsorbent Polymer with Metal Ions: An Undergraduate Chemistry Experiment

ERIC Educational Resources Information Center

Yaung, Jing-Fun; Chen, Yueh-Huey

2009-01-01

A novel undergraduate chemistry experiment involving superabsorbent polymers commonly used in diapers and other personal care products is described. Students observe the removal of divalent transition-metal ions from aqueous solutions by the polymers. With the procedures provided, students are able to color the superabsorbent polymers with metal…

A Comprehensive General Chemistry Demonstration

ERIC Educational Resources Information Center

Sweeder, Ryan D.; Jeffery, Kathleen A.

2013-01-01

This article describes the use of a comprehensive demonstration suitable for a high school or first-year undergraduate introductory chemistry class. The demonstration involves placing a burning candle in a container adjacent to a beaker containing a basic solution with indicator. After adding a lid, the candle will extinguish and the produced…

The chemistry of salt-affected soils and waters

USDA-ARS?s Scientific Manuscript database

Knowledge of the chemistry of salt affected soils and waters is necessary for management of irrigation in arid and semi-arid regions. In this chapter we review the origin of salts in the landscape, the major chemical reactions necessary for prediction of the soil solution composition, and the use of...

Solute-specific patterns and drivers of urban stream chemistry revealed by long-term monitoring in Baltimore, Maryland

NASA Astrophysics Data System (ADS)

Reisinger, A. J.; Woytowitz, E.; Majcher, E.; Rosi, E. J.; Groffman, P.

2017-12-01

Urban streams receive a myriad of chemical inputs from the surrounding landscape due to altered lithology (asphalt, concrete), leaky sewage infrastructure, and other human activities (road salt, fertilizer, industrial wastes, wastewater effluent), potentially leading to multiple chemical stressors occurring simultaneously. To evaluate potential drivers of water chemistry change, we used approximately 20 years of weekly water chemistry monitoring data from streams in the Baltimore Ecosystem Study (BES) to quantify trends of annual loads and flow-weighted concentrations for multiple solutes of interest, including nitrate (NO3-), phosphate (PO43-), total nitrogen (TN), total phosphorus (TP), chloride (Cl-), and sulfate (SO42-) and subsequently examined various gray and green infrastructure characteristics at the watershed scale. For example, we quantified annual volume and duration of reported sanitary sewer overflows (SSO) and cumulative storage volume and area of various best management practices (BMPs). Site- and solute-specific trends differed, but across our monitoring network we found evidence for decreasing annual export for multiple solutes. Additionally, we found that changes in gray- and green-infrastructure characteristics were related to changes in water quality at our most downstream (most urban) monitoring site. For example, annual NO3- loads increased with longer cumulative SSO duration, whereas annual PO43- and TP loads decreased with a cumulative BMP area in the watershed. Further, we used same long-term water chemistry data and multivariate analyses to investigate whether urban streams have unique water chemistry fingerprints representing the multiple chemical stressors at a given site, which could provide insight into sources and impacts of water-quality impairment. These analyses and results illustrate the major role gray and green infrastructure play in influencing water quality in urban environments, and illustrate that focusing on a variety of chemical stressors is necessary to gain a broader understanding of the issues affecting urban water quality.

Degradation of Highly Alloyed Metal Halide Perovskite Precursor Inks: Mechanism and Storage Solutions

DOE PAGES

Dou, Benjia; Wheeler, Lance M.; Christians, Jeffrey A.; ...

2018-03-14

Whereas the promise of metal halide perovskite (MHP) photovoltaics (PV) is that they can combine high efficiency with solution-processability, the chemistry occurring in precursor inks is largely unexplored. Herein, we investigate the degradation of MHP solutions based on the most widely used solvents, dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). For the MHP inks studied, which contain formamidinium (FA+), methylammonium (MA+), cesium (Cs+), lead (Pb2+), bromide (Br-), and iodide (I-), dramatic compositional changes are observed following storage of the inks in nitrogen in the dark. We show that hydrolysis of DMF in the precursor solution forms dimethylammonium formate, which subsequently incorporatesmore » into the MHP film to compromise the ability of Cs+ and MA+ to stabilize FA+-based MHP. The changes in solution chemistry lead to a modification of the perovskite film stoichiometry, band gap, and structure. The solid precursor salts are stable when ball-milled into a powder, allowing for the storage of large quantities of stoichiometric precursor materials.« less

Enhancing boron rejection in FO using alkaline draw solutions.

PubMed

Wang, Yi-Ning; Li, Weiyi; Wang, Rong; Tang, Chuyang Y

2017-07-01

This study provides a novel method to enhance boron removal in a forward osmosis (FO) process. It utilizes the reverse solute diffusion (RSD) of ions from alkaline draw solutions (DSs) and the concentration polarization of the hydroxyl ions to create a highly alkaline environment near the membrane active surface. The results show that boron rejection can be significantly enhanced by increasing the pH of NaCl DS to 12.5 in the active-layer-facing-feed-solution (AL-FS) orientation. The effect of RSD enhanced boron rejection was further promoted in the presence of concentration polarization (e.g., in the active-layer-facing-draw-solution (AL-DS) orientation). The current study opens a new dimension for controlling contaminant removal by FO using tailored DS chemistry, where the RSD-induced localized water chemistry change is taken advantage in contrast to the conventional method of chemical dosing to the bulk feed water. Copyright © 2017 Elsevier Ltd. All rights reserved.

Degradation of Highly Alloyed Metal Halide Perovskite Precursor Inks: Mechanism and Storage Solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dou, Benjia; Wheeler, Lance M.; Christians, Jeffrey A.

Whereas the promise of metal halide perovskite (MHP) photovoltaics (PV) is that they can combine high efficiency with solution-processability, the chemistry occurring in precursor inks is largely unexplored. Herein, we investigate the degradation of MHP solutions based on the most widely used solvents, dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). For the MHP inks studied, which contain formamidinium (FA+), methylammonium (MA+), cesium (Cs+), lead (Pb2+), bromide (Br-), and iodide (I-), dramatic compositional changes are observed following storage of the inks in nitrogen in the dark. We show that hydrolysis of DMF in the precursor solution forms dimethylammonium formate, which subsequently incorporatesmore » into the MHP film to compromise the ability of Cs+ and MA+ to stabilize FA+-based MHP. The changes in solution chemistry lead to a modification of the perovskite film stoichiometry, band gap, and structure. The solid precursor salts are stable when ball-milled into a powder, allowing for the storage of large quantities of stoichiometric precursor materials.« less

[Dissolved aluminum and organic carbon in soil solution under six tree stands in Lushan forest ecosystems].

PubMed

Wang, Lianfeng; Pan, Genxing; Shi, Shengli; Zhang, Lehua; Huang, Mingxing

2003-10-01

Different depths of soils under 6 tree stands in Lushan Botany Garden were sampled and water-digested at room temperature. The dissolved aluminum and organic carbon were then determined by colorimetry, using 8-hydroxylquilin and TOC Analyzer, respectively. The results indicated that even derived from a naturally identical soil type, the test soils exhibited a diverse solution chemistry, regarding with the Al speciation. The soil solutions under Japanese cedar, giant arborvitae and tea had lower pH values and higher contents of soluble aluminum than those under Giant dogwood, azalea and bamboo. Under giant arborvitae, the lowest pH and the highest content of total soluble aluminum and monomeric aluminum were found in soil solution. There was a significant correlation between soluble aluminum and DOC, which tended to depress the accumulation of toxic monomeric aluminum. The 6 tree stands could be grouped into 2 categories of solution chemistry, according to aluminum mobilization.

Effect of surface chemistries and characteristics of Ti6Al4V on the Ca and P adsorption and ion dissolution in Hank's ethylene diamine tetra-acetic acid solution.

PubMed

Chang, E; Lee, T M

2002-07-01

This study examined the influence of chemistries and surface characteristics of Ti6Al4V on the adsorption of Ca and P species and ion dissolution behavior of the material exposed in Hank's solution with 8.0 mM ethylene diamine tetra-acetic acid at 37 degrees C. The variation of chemistries of the alloy and nano-surface characteristics (chemistries of nano-surface oxides, amphoteric OH group adsorbed on oxides, and oxide thickness) was effected by surface modification and three passivation methods (34% nitric acid passivation. 400 degrees C heated in air, and aged in 100 degrees C water). X-ray photoelectron spectroscopy and Auger electron spectroscopy were used for surface analyses. The chemistries of nano-surface oxides in a range studied should not change the capability of Ca and P adsorption. Nor is the capability affected significantly by amphoteric OH group and oxide thickness. However, passivations influence the surface oxide thickness and the early stage ion dissolution rate of the alloy. The rate-limiting step of the rate can be best explained by metal-ion transport through the oxide film, rather than hydrolysis of the film. Variation of the chemistries of titanium alloy alters the electromotive force potential of the metal, thereby affecting the corrosion and ion dissolution rate.

Comparison of Chain Conformation of Poly(vinyl alcohol) in Solutions and Melts from Quantum Chemistry Based Molecular Dynamics Simulations

NASA Technical Reports Server (NTRS)

Jaffe, Richard; Han, Jie; Matsuda, Tsunetoshi; Yoon, Do; Langhoff, Stephen R. (Technical Monitor)

1997-01-01

Confirmations of 2,4-dihydroxypentane (DHP), a model molecule for poly(vinyl alcohol), have been studied by quantum chemistry (QC) calculations and molecular dynamics (MD) simulations. QC calculations at the 6-311G MP2 level show the meso tt conformer to be lowest in energy followed by the racemic tg, due to intramolecular hydrogen bond between the hydroxy groups. The Dreiding force field has been modified to reproduce the QC conformer energies for DHP. MD simulations using this force field have been carried out for DHP molecules in the gas phase, melt, and CHCl3 and water solutions. Extensive intramolecular hydrogen bonding is observed for the gas phase and CHCl3 solution, but not for the melt or aqueous solution, Such a condensed phase effect due to intermolecular interactions results in a drastic change in chain conformations, in agreement with experiments.

Surface complexation of carboxylate adheres Cryptosporidium parvum öocysts to the hematite-water interface

USGS Publications Warehouse

Gao, X.; Metge, D.W.; Ray, C.; Harvey, R.W.; Chorover, J.

2009-01-01

The interaction of viable Cryptosporidium parvum öocysts at the hematite (α-Fe2O3)−water interface was examined over a wide range in solution chemistry using in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. Spectra for hematite-sorbed öocysts showed distinct changes in carboxylate group vibrations relative to spectra obtained in the absence of hematite, indicative of direct chemical bonding between carboxylate groups and Fe metal centers of the hematite surface. The data also indicate that complexation modes vary with solution chemistry. In NaCl solution, öocysts are bound to hematite via monodentate and binuclear bidentate complexes. The former predominates at low pH, whereas the latter becomes increasingly prevalent with increasing pH. In a CaCl2 solution, only binuclear bidentate complexes are observed. When solution pH is above the point of zero net proton charge (PZNPC) of hematite, öocyst surface carboxylate groups are bound to the mineral surface via outer-sphere complexes in both electrolyte solutions.

Effect of oxidation state and ionic strength on sorption of actinides (Th, U, Np, Am) to geologic media [Abstract and References Only

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dittrich, Timothy M.; Richmann, Michael K.; Reed, Donald T.

2015-10-30

The degree of conservatism in the estimated sorption partition coefficients (K ds) used in a performance assessment model is being evaluated based on a complementary batch and column method. The main focus of this work is to investigate the role of ionic strength, solution chemistry, and oxidation state (III-VI) in actinide sorption to dolomite rock. Based on redox conditions and solution chemistry expected at the WIPP, possible actinide species include Pu(III), Pu(IV), U(IV), U(VI), Np(IV), Np(V), Am(III), and Th(IV).

Characterisation of Crevice and Pit Solution Chemistries Using Capillary Electrophoresis with Contactless Conductivity Detector

PubMed Central

Nie, Mengyan; Wharton, Julian A.; Cranny, Andy; Harris, Nick R.; Wood, Robert J.K.; Stokes, Keith R.

2013-01-01

The ability to predict structural degradation in-service is often limited by a lack of understanding of the evolving chemical species occurring within a range of different microenvironments associated with corrosion sites. Capillary electrophoresis (CE) is capable of analysing nanolitre solution volumes with widely disparate concentrations of ionic species, thereby producing accurate and reliable results for the analysis of the chemical compositions found within microenvironment corrosion solutions, such as those found at crevice and pit corrosion sites. In this study, CE with contactless conductivity detection (CCD) has been used to characterize pitting and crevice corrosion solution chemistries for the first time. By using the capillary electrophoresis with contactless conductivity detection (CE-CCD) system, direct and simultaneous detection of seven metal cations (Cu2+, Ni2+, Fe3+, Fe2+, Cr3+, Mn2+, and Al3+) and chloride anions was achieved with a buffer solution of 10 mM 2,6-pyridinedicarboxylic acid and 0.5 mM cetyltrimethylammonium hydroxide at pH 4 using a pre-column complexation method. The detection limits obtained for the metal cations and chloride anions were 100 and 10 ppb, respectively. The CE-CCD methodology has been demonstrated to be a versatile technique capable of speciation and quantifying the ionic species generated within artificial pit (a pencil electrode) and crevice corrosion geometries for carbon steels and nickel-aluminium bronze, thus allowing the evolution of the solution chemistry to be assessed with time and the identification of the key corrosion analyte targets for structural health monitoring. PMID:28788335

A Polymer "Pollution Solution" Classroom Activity.

ERIC Educational Resources Information Center

Helser, Terry L.

1996-01-01

Explains an approach to presenting polymer chemistry to nonmajors that employs polystyrene foam, foam peanuts made from water soluble starch, and water soluble plastic bags. Students are presented with a pollution scenario and are guided to the discovery of solutions. (DDR)

40 Low-Waste, Low-Risk Chemistry Labs.

ERIC Educational Resources Information Center

Dougan, David

This resource book contains 40 chemistry labs and provides a single solution to the problems of purchase, storage, use, and disposal of chemicals. The text is designed to be used alone or integrated with current textbooks. A mixture of microchemistry and macrochemistry is used to provide variety and reflects trends in research and industry. Most…

Raising Environmental Awareness through Applied Biochemistry Laboratory Experiments

ERIC Educational Resources Information Center

Salman Ashraf, S.

2013-01-01

Our environment is under constant pressure and threat from various sources of pollution. Science students, in particular chemistry students, must not only be made aware of these issues, but also be taught that chemistry (and science) can provide solutions to such real-life issues. To this end, a newly developed biochemistry laboratory experiment…

Hydrology and Species-Specific Effects of Bacopa monnieri and Leersia oryzoides on Soil and Water Chemistry

USDA-ARS?s Scientific Manuscript database

In an eight week greenhouse experiment, Bacopa monnieri (Water Hyssop) and Leersia oryzoides (Rice Cutgrass) were compared for nutrient assimilation as well as soil and water chemistry under variable flooding regimes using a nutrient solution rich in nitrogen (N) and phosphorus (P). Soil redox poten...

Chemistry [Sahuarita High School Career Curriculum Project].

ERIC Educational Resources Information Center

Lane, Robert

This course entitled "Chemistry" is one of a series of instructional guides prepared by teachers for the Sahuarita High School (Arizona) Career Curriculum Project. It consists of three packages, the first dealing with solids, liquids and solutions, the second with acids, bases and anions, and the third with cation analysis. These packages are…

Understanding "Green Chemistry" and "Sustainability": An Example of Problem-Based Learning (PBL)

ERIC Educational Resources Information Center

Günter, Tugçe; Akkuzu, Nalan; Alpat, Senol

2017-01-01

Background: This study uses problem-based learning (PBL) to ensure that students comprehend the significance of green chemistry better by experiencing the stages of identifying the problem, developing hypotheses, and providing solutions within the problem-solving process. Purpose: The aim of this study is to research the effect of PBL implemented…

Advanced Chemistry for Operators. Training Module 1.321.3.77.

ERIC Educational Resources Information Center

Kirkwood Community Coll., Cedar Rapids, IA.

This document is an instructional module package prepared in objective form for use by an instructor familiar with inorganic and general organic chemistry as applied to water and wastewater treatment. Included are objectives, instructor guides, and student handouts. The module contains material related to chemical reactions in water solutions,…

Environmental chemistry at vapor/water interfaces: insights from vibrational sum frequency generation spectroscopy.

PubMed

Jubb, Aaron M; Hua, Wei; Allen, Heather C

2012-01-01

The chemistry that occurs at surfaces has been an intense area of study for many years owing to its complexity and importance in describing a wide range of physical phenomena. The vapor/water interface is particularly interesting from an environmental chemistry perspective as this surface plays host to a wide range of chemistries that influence atmospheric and geochemical interactions. The application of vibrational sum frequency generation (VSFG), an inherently surface-specific, even-order nonlinear optical spectroscopy, enables the direct interrogation of various vapor/aqueous interfaces to elucidate the behavior and reaction of chemical species within the surface regime. In this review we discuss the application of VSFG to the study of a variety of atmospherically important systems at the vapor/aqueous interface. Chemical systems presented include inorganic ionic solutions prevalent in aqueous marine aerosols, small molecular solutes, and long-chain fatty acids relevant to fat-coated aerosols. The ability of VSFG to probe both the organization and reactions that may occur for these systems is highlighted. A future perspective toward the application of VSFG to the study of environmental interfaces is also provided.

A Wet Chemistry Laboratory Cell

NASA Technical Reports Server (NTRS)

2008-01-01

This picture of NASA's Phoenix Mars Lander's Wet Chemistry Laboratory (WCL) cell is labeled with components responsible for mixing Martian soil with water from Earth, adding chemicals and measuring the solution chemistry. WCL is part of the Microscopy, Electrochemistry, and Conductivity Analyzer (MECA) instrument suite on board the Phoenix lander.

The Phoenix Mission is led by the University of Arizona, Tucson, on behalf of NASA. Project management of the mission is by NASA's Jet Propulsion Laboratory, Pasadena, Calif. Spacecraft development is by Lockheed Martin Space Systems, Denver.

A note on the chemistry of seawater in the range 350°-500°C

USGS Publications Warehouse

Bischoff, James L.; Rosenbauer, Robert J.

1983-01-01

The chemistry of seawater at conditions of 350° to 500°C, 220 to 1000 bars (22 to 100 MPa) is controlled by reactions involving magnesium hydroxide sulfate (MHSH) and anhydrite. During progressive heating from 350° to 500°C at 1000 bars (100 MPa), MHSH with a  ratio of 1.25 is formed via precipitation from solution and via reaction of solution with pre-existing anhydrite. During adiabatic expansion the MHSH extracts additional SO4 from seawater and converts to a stoichiometry in which . These reactions control and greatly change the concentrations of Ca, Mg, SO4 in solution and produce significant ionizable hydrogen, attaining 11.7 mmoles kg−1 at maximum conditions.

Synthesis of Bimetallic Platinum Nanoparticles for Biosensors

PubMed Central

Leteba, Gerard M.; Lang, Candace I.

2013-01-01

The use of magnetic nanomaterials in biosensing applications is growing as a consequence of their remarkable properties; but controlling the composition and shape of metallic nanoalloys is problematic when more than one precursor is required for wet chemistry synthesis. We have developed a successful simultaneous reduction method for preparation of near-spherical platinum-based nanoalloys containing magnetic solutes. We avoided particular difficulties in preparing platinum nanoalloys containing Ni, Co and Fe by the identification of appropriate synthesis temperatures and chemistry. We used transmission electron microscopy (TEM) to show that our particles have a narrow size distribution, uniform size and morphology, and good crystallinity in the as-synthesized condition. Energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) confirms the coexistence of Pt with the magnetic solute in a face-centered cubic (FCC) solid solution. PMID:23941910

Evolution of Iodoplumbate Complexes in Methylammonium Lead Iodide Perovskite Precursor Solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sharenko, Alexander; Mackeen, Cameron; Jewell, Leila

Here in this study we investigate the local structure present in single-step precursor solutions of methylammonium lead iodide (MAPbI 3) perovskite as a function of organic and inorganic precursor ratio, as well as with hydriodic acid (HI), using X-ray absorption spectroscopy. An excess of organic precursor as well as the use of HI as a processing additive has been shown to lead to the formation of smooth, continuous, pinhole free MAPbI 3 films, whereas films produced from precursor solutions containing molar equivalents of methylammonium iodide (MAI) and PbI 2 lead to the formation of a discontinuous, needlelike morphology. We nowmore » show that as the amount of excess MAI in the precursor solution is increased, the iodide coordination of iodoplumbate complexes present in solution increases. The use of HI results in a similar increase in iodide coordination. We therefore offer insight into how solution chemistry can be used to control MAPbI 3 thin film morphology by revealing a strong correlation between the lead coordination chemistry in precursor solutions and the surface coverage and morphology of the resulting MAPbI 3 film.« less

Evolution of Iodoplumbate Complexes in Methylammonium Lead Iodide Perovskite Precursor Solutions

DOE PAGES

Sharenko, Alexander; Mackeen, Cameron; Jewell, Leila; ...

2017-02-02

Here in this study we investigate the local structure present in single-step precursor solutions of methylammonium lead iodide (MAPbI 3) perovskite as a function of organic and inorganic precursor ratio, as well as with hydriodic acid (HI), using X-ray absorption spectroscopy. An excess of organic precursor as well as the use of HI as a processing additive has been shown to lead to the formation of smooth, continuous, pinhole free MAPbI 3 films, whereas films produced from precursor solutions containing molar equivalents of methylammonium iodide (MAI) and PbI 2 lead to the formation of a discontinuous, needlelike morphology. We nowmore » show that as the amount of excess MAI in the precursor solution is increased, the iodide coordination of iodoplumbate complexes present in solution increases. The use of HI results in a similar increase in iodide coordination. We therefore offer insight into how solution chemistry can be used to control MAPbI 3 thin film morphology by revealing a strong correlation between the lead coordination chemistry in precursor solutions and the surface coverage and morphology of the resulting MAPbI 3 film.« less

Solution based zinc tin oxide TFTs: the dual role of the organic solvent

NASA Astrophysics Data System (ADS)

Salgueiro, Daniela; Kiazadeh, Asal; Branquinho, Rita; Santos, Lídia; Barquinha, Pedro; Martins, Rodrigo; Fortunato, Elvira

2017-02-01

Chemical solution deposition is a low cost, scalable and high performance technique to obtain metal oxide thin films. Recently, solution combustion synthesis has been introduced as a chemical route to reduce the processing temperature. This synthesis method takes advantage of the chemistry of the precursors as a source of energy for localized heating. According to the combustion chemistry some organic solvents can have a dual role in the reaction, acting both as solvent and fuel. In this work, we studied the role of 2-methoxyethanol in solution based synthesis of ZTO thin films and its influence on the performance of ZTO TFTs. The thermal behaviour of ZTO precursor solutions confirmed that 2-methoxyethanol acts simultaneously as a solvent and fuel, replacing the fuel function of urea. The electrical characterization of the solution based ZTO TFTs showed a slightly better performance and lower variability under positive gate bias stress when urea was not used as fuel, confirming that the excess fuel contributes negatively to the device operation and stability. Solution based ZTO TFTs demonstrated a low hysteresis (ΔV  =  -0.3 V) and a saturation mobility of 4-5 cm2 V-1 s-1.

Landscape linkages between geothermal activity and solute composition and ecological response in surface waters draining the Atlantic slope of Costa Rica

USGS Publications Warehouse

Pringle, Catherine M.; Rowe, Gary L.; Triska, Frank J.; Fernandez, Jose F.; West, John

1993-01-01

Surface waters draining three different volcanoes in Costa Rica, ranging from dormant to moderately active to explosive, have a wide range of solute compositions that partly reflects the contribution of different types of solute-rich, geothermal waters. Three major physical transport vectors affect flows of geothermally derived solutes: thermally driven convection of volcanic gases and geothermal fluids; lateral and gravity-driven downward transport of geothermal fluids; and wind dispersion of ash, gases, and acid rain. Specific vector combinations interact to determine landscape patterns in solute chemistry and biota: indicator taxa of algae and bacteria reflect factors such as high temperature, wind-driven or hydrologically transported acidity, high concentrations of various solutes, and chemical precipitation reactions. Many streams receiving geothermally derived solutes have high levels of soluble reactive phosphorus (SRP) (up to 400 µg liter−1), a nutrient that is typically not measured in geochemical studies of geothermal waters. Regional differences in levels of SRP and other solutes among volcanoes were typically not significant due to high local variation in solute levels among geothermally modified streams and between geothermally modified and unmodified streams on each volcano. Geothermal activity along the volcanic spine of Costa Rica provides a natural source of phosphorus, silica, and other solutes and plays an important role in determining emergent landscape patterns in the solute chemistry of surface waters and aquatic biota.

Development of Scientific Approach Based on Discovery Learning Module

NASA Astrophysics Data System (ADS)

Ellizar, E.; Hardeli, H.; Beltris, S.; Suharni, R.

2018-04-01

Scientific Approach is a learning process, designed to make the students actively construct their own knowledge through stages of scientific method. The scientific approach in learning process can be done by using learning modules. One of the learning model is discovery based learning. Discovery learning is a learning model for the valuable things in learning through various activities, such as observation, experience, and reasoning. In fact, the students’ activity to construct their own knowledge were not optimal. It’s because the available learning modules were not in line with the scientific approach. The purpose of this study was to develop a scientific approach discovery based learning module on Acid Based, also on electrolyte and non-electrolyte solution. The developing process of this chemistry modules use the Plomp Model with three main stages. The stages are preliminary research, prototyping stage, and the assessment stage. The subject of this research was the 10th and 11th Grade of Senior High School students (SMAN 2 Padang). Validation were tested by the experts of Chemistry lecturers and teachers. Practicality of these modules had been tested through questionnaire. The effectiveness had been tested through experimental procedure by comparing student achievement between experiment and control groups. Based on the findings, it can be concluded that the developed scientific approach discovery based learning module significantly improve the students’ learning in Acid-based and Electrolyte solution. The result of the data analysis indicated that the chemistry module was valid in content, construct, and presentation. Chemistry module also has a good practicality level and also accordance with the available time. This chemistry module was also effective, because it can help the students to understand the content of the learning material. That’s proved by the result of learning student. Based on the result can conclude that chemistry module based on discovery learning and scientific approach in electrolyte and non-electrolyte solution and Acid Based for the 10th and 11th grade of senior high school students were valid, practice, and effective.

Solute sources in stream water during consecutive fall storms in a northern hardwood forest watershed: A combined hydrological, chemical and isotopic approach

USGS Publications Warehouse

Mitchell, M.J.; Piatek, K.B.; Christopher, S.; Mayer, B.; Kendall, C.; McHale, P.

2006-01-01

Understanding the effects of climate change including precipitation patterns has important implications for evaluating the biogeochemical responses of watersheds. We focused on four storms in late summer and early fall that occurred after an exceptionally dry period in 2002. We analyzed not only the influence of these storms on episodic chemistry and the role of different water sources in affecting surface water chemistry, but also the relative contributions of these storms to annual biogeochemical mass balances. The study site was a well studied 135-ha watershed in the Adirondack Park of New York State (USA). Our analyses integrated measurements on hydrology, solute chemistry and the isotopic composition of NO 3- (??15N and ??18O) and SO 42- (??34S and ??18O) to evaluate how these storms affected surface water chemistry. Precipitation amounts varied among the storms (Storm 1: Sept. 14-18, 18.5 mm; Storm 2: Sept. 21-24, 33 mm; Storm 3: Sept. 27-29, 42.9 mm; Storm 4: Oct. 16-21, 67.6 mm). Among the four storms, there was an increase in water yields from 2 to 14%. These water yields were much less than in studies of storms in previous years at this same watershed when antecedent moisture conditions were higher. In the current study, early storms resulted in relatively small changes in water chemistry. With progressive storms the changes in water chemistry became more marked with particularly major changes in Cb (sum of base cations), Si, NO 3- , and SO 42- , DOC and pH. Analyses of the relationships between Si, DOC, discharge and water table height clearly indicated that there was a decrease in ground water contributions (i.e., lower Si concentrations and higher DOC concentrations) as the watershed wetness increased with storm succession. The marked changes in chemistry were also reflected in changes in the isotopic composition of SO 42- and NO 3- . There was a strong inverse relationship between SO 42- concentrations and ??34S values suggesting the importance of S biogeochemical redox processes in contributing to SO 42- export. The isotopic composition of NO 3- in stream water indicated that this N had been microbially processed. Linkages between SO 42- and DOC concentrations suggest that wetlands were major sources of these solutes to drainage waters while the chemical and isotopic response of NO 3- suggested that upland sources were more important. Although these late summer and fall storms did not play a major role in the overall annual mass balances of solutes for this watershed, these events had distinctive chemistry including depressed pH and therefore have important consequences to watershed processes such as episodic acidification, and the linkage of these processes to climate change. ?? Springer 2006.

Improving Pharmacy Students' Understanding and Long-term Retention of Acid-Base Chemistry

PubMed Central

2007-01-01

Despite repeated exposure to the principles underlying the behavior of organic acids and bases in aqueous solution, some pharmacy students remain confused about the topic of acid-base chemistry. Since a majority of organic drug molecules have acid-base character, the ability to predict their reactivity and the extent to which they will ionize in a given medium is paramount to students' understanding of essentially all aspects of drug action in vivo and in vitro. This manuscript presents a medicinal chemistry lesson in the fundamentals of acid-base chemistry that many pharmacy students have found enlightening and clarifying PMID:19503706

An implicit semianalytic numerical method for the solution of nonequilibrium chemistry problems

NASA Technical Reports Server (NTRS)

Graves, R. A., Jr.; Gnoffo, P. A.; Boughner, R. E.

1974-01-01

The first order differential equation form systems of equations. They are solved by a simple and relatively accurate implicit semianalytic technique which is derived from a quadrature solution of the governing equation. This method is mathematically simpler than most implicit methods and has the exponential nature of the problem embedded in the solution.

Lysozyme pattern formation in evaporating droplets

NASA Astrophysics Data System (ADS)

Gorr, Heather Meloy

Liquid droplets containing suspended particles deposited on a solid, flat surface generally form ring-like structures due to the redistribution of solute during evaporation (the "coffee ring effect"). The forms of the deposited patterns depend on complex interactions between solute(s), solvent, and substrate in a rapidly changing, far from equilibrium system. Solute self-organization during evaporation of colloidal sessile droplets has attracted the attention of researchers over the past few decades due to a variety of technological applications. Recently, pattern formation during evaporation of various biofluids has been studied due to potential applications in medical screening and diagnosis. Due to the complexity of 'real' biological fluids and other multicomponent systems, a comprehensive understanding of pattern formation during droplet evaporation of these fluids is lacking. In this PhD dissertation, the morphology of the patterns remaining after evaporation of droplets of a simplified model biological fluid (aqueous lysozyme solutions + NaCl) are examined by atomic force microscopy (AFM) and optical microscopy. Lysozyme is a globular protein found in high concentration, for example, in human tears and saliva. The drop diameters, D, studied range from the micro- to the macro- scale (1 microm -- 2 mm). In this work, the effect of evaporation conditions, solution chemistry, and heat transfer within the droplet on pattern formation is examined. In micro-scale deposits of aqueous lysozyme solutions (1 microm < D < 50 microm), the protein motion and the resulting dried residue morphology are highly influenced by the decreased evaporation time of the drop. The effect of electrolytes on pattern formation is also investigated by adding varying concentrations NaCl to the lysozyme solutions. Finally, a novel pattern recognition program is described and implemented which classifies deposit images by their solution chemistries. The results presented in this PhD dissertation provide insight into the evaporative behavior and pattern formation in droplets of simplified model biological fluids (aqueous lysozyme + NaCl). The patterns that form depend sensitively on the evaporation conditions, characteristic time and length scales, and the physiochemical properties of the solutions. The patterns are unique, dependent on solution chemistry, and may therefore act as a "fingerprint" in identifying fluid properties.

Relationships among foliar chemistry, foliar polyamines, and soil chemistry in red spruce trees growing across the northeastern United States

USGS Publications Warehouse

Minocha, R.; Shortle, W.C.; Lawrence, G.B.; David, M.B.; Minocha, S.C.

1997-01-01

Forest trees are constantly exposed to various types of natural and anthropogenic stressors. A major long-term goal of our research is to develop a set of early physiological and biochemical markers of stress in trees before the appearance of visual symptoms. Six red spruce (Picea rubens Sarg.) stands from the northeastern United States were selected for collection of soil and foliage samples. All of the chosen sites had soil solution pH values below 4.0 in the Oa horizon but varied in their geochemistry. Some of these sites were apparently under some form of environmental stress as indicated by a large number of dead and dying red spruce trees. Samples of soil and needles (from apparently healthy red spruce trees) were collected from these sites four times during a two-year period. The needles were analyzed for perchloric acid-soluble polyamines and exchangeable inorganic ions. Soil and soil solution samples from the Oa and B horizons were analyzed for their exchange chemistry. The data showed a strong positive correlation between Ca and Mg concentrations in the needles and in the Oa horizon of the soil. However, needles from trees growing on relatively Ca-rich soils with a low exchangeable Al concentration and a low Al:Ca soil solution ratio had significantly lower concentrations of putrescine and spermidine than those growing on Ca-poor soils with a high exchangeable Al concentration and a high Al:Ca soil solution in the Oa horizon. The magnitude of this change was several fold higher for putrescine concentrations than for spermidine concentrations. Neither putrescine nor spermidine were correlated with soil solution Ca, Mg, and Al concentrations in the B horizon. The putrescine concentrations of the needles always correlated significantly with exchangeable Al (r2=0.73, p???0.05) and still solution Al:Ca ratios (r2=0.91, p???0.01) of the Oa horizon. This suggests that in conjunction with soil chemistry, putrescine and/or spermidine may be used as a potential early indicator of Al stress before the appearance of visual symptoms in red spruce trees.

Exploring Dominant Types of Explanations Built by General Chemistry Students

ERIC Educational Resources Information Center

Talanquer, Vicente

2010-01-01

The central goal of our study was to explore the nature of the explanations generated by science and engineering majors with basic training in chemistry to account for the colligative properties of solutions. The work was motivated by our broader interest in the characterisation of the dominant types of explanations that science college students…

Instrumental Techniques in Archeological Research

DTIC Science & Technology

1988-09-01

and instruments borrowed from the fields of chemistry , physics, geology, metallurgy, and ceramic engineering yield quantitative data on archeological...artifacts. Early analyses relied primarily on wet chemistry techniques in which samples of artifacts were dissolved into liquid solutions, destroying...other organic and inorganic materials. Advantages and disadvantages are dis- cussed. Each technique is presented with attention to appropriate materials

The Quantitative Resolution of a Mixture of Group II Metal Ions by Thermometric Titration with EDTA. An Analytical Chemistry Experiment.

ERIC Educational Resources Information Center

Smith, Robert L.; Popham, Ronald E.

1983-01-01

Presents an experiment in thermometric titration used in an analytic chemistry-chemical instrumentation course, consisting of two titrations, one a mixture of calcium and magnesium, the other of calcium, magnesium, and barium ions. Provides equipment and solutions list/specifications, graphs, and discussion of results. (JM)

A Simple Experiment in the Separation of a Solid-Phase Mixture and Infrared Spectroscopy for Introductory Chemistry

ERIC Educational Resources Information Center

Szalay, Paul S.

2008-01-01

This experiment was developed as a means of incorporating instrumental analyses into an introductory chemistry laboratory. A two-component solid mixture of caffeine and ibuprofen is separated through a series of solution extractions and precipitation and their relative amounts measured. These compounds were chosen because the combination of…

Development of an Augmented Reality Game to Teach Abstract Concepts in Food Chemistry

ERIC Educational Resources Information Center

Crandall, Philip G.; Engler, Robert K.; Beck, Dennis E.; Killian, Susan A.; O'Bryan, Corliss A.; Jarvis, Nathan; Clausen, Ed

2015-01-01

One of the most pressing issues for many land grant institutions is the ever increasing cost to build and operate wet chemistry laboratories. A partial solution is to develop computer-based teaching modules that take advantage of animation, web-based or off-campus learning experiences directed at engaging students' creative experiences. We…

Fullerene Transport in Saturated Porous Media

EPA Science Inventory

We investigated the effects of background solution chemistry and residence time within the soil column on the transport of aqu/C60 through saturated ultrapure quartz sand columns. Aqu/C60 breakthrough curves were obtained under different pore water velocities, solution pHs, and i...

A comparison of amorphous calcium carbonate crystallization in aqueous solutions of MgCl2 and MgSO4: implications for paleo-ocean chemistry

NASA Astrophysics Data System (ADS)

Han, Mei; Zhao, Yanyang; Zhao, Hui; Han, Zuozhen; Yan, Huaxiao; Sun, Bin; Meng, Ruirui; Zhuang, Dingxiang; Li, Dan; Liu, Binwei

2018-04-01

Based on the terminology of "aragonite seas" and "calcite seas", whether different Mg sources could affect the mineralogy of carbonate sediments at the same Mg/Ca ratio was explored, which was expected to provide a qualitative assessment of the chemistry of the paleo-ocean. In this work, amorphous calcium carbonate (ACC) was prepared by direct precipitation in anhydrous ethanol and used as a precursor to study crystallization processes in MgSO4 and MgCl2 solutions having different concentrations at 60 °C (reaction times 240 and 2880 min). Based on the morphology of the aragonite crystals, as well as mineral saturation indices and kinetic analysis of geochemical processes, it was found that these crystals formed with a spherulitic texture in 4 steps. First, ACC crystallized into columnar Mg calcite by nearly oriented attachment. Second, the Mg calcite changed from columnar shapes into smooth dumbbell forms. Third, the Mg calcite transformed into rough dumbbell or cauliflower-shaped aragonite forms by local dissolution and precipitation. Finally, the aragonite transformed further into spherulitic radial and irregular aggregate forms. The increase in Ca2+ in the MgSO4 solutions compared with the MgCl2 solutions indicates the fast dissolution and slow precipitation of ACC in the former solutions. The phase transition was more complete in the 0.005 M MgCl2 solution, whereas Mg calcite crystallized from the 0.005 M MgSO4 solution, indicating that Mg calcite could be formed more easily in an MgSO4 solution. Based on these findings, aragonite and Mg calcite relative to ACC could be used to provide a qualitative assessment of the chemistry of the paleo-ocean. Therefore, calcite seas relative to high-Mg calcite could reflect a low concentration MgSO4 paleo-ocean, while aragonite seas could be related to an MgCl2 or high concentration of MgSO4 paleo-ocean.

The Effect of Solution Chemistry on Nucleation of Nesquehonite

NASA Astrophysics Data System (ADS)

Zhao, L.; Zhu, C.; Wang, Z.

2016-12-01

The interfaces between minerals and aqueous solutions are key to important Earth surface processes, including chemical weathering, mineral dissolution/precipitation, and pollutant absorption/release. Mineral surface properties, such as the surface structure and the surface energy, determine the outcomes of many geochemical reactions. Several factors could affect surface energy, but the effect of solution chemistry, particularly the solution stoichiometry, on the surface energy and nucleation process is poorly understood. The goal of this study is to understand the effect of solution chemistry on the nucleation of nesquehonite. Nesquehonite nucleation experiments were conducted in aqueous solutions having similar Mg2+/ CO32- activity ratios, but different saturation states and solution pH. The experimental results show that induction-time estimates from our precipitation experiments with similar Mg2+/CO32- activity ratios are consistent with classical nucleation theory (CNT), while the surface energy derived from CNT varies with Mg2+/CO32- activity ratios. Our observations can be explained by the different absorption behaviors of Mg2+ and CO32- and and/or reduced Gibbs free energies through better screening of the electric double layer. A surface energy model involving solution composition is developed that combines surface complexation with electrostatic models. The new model takes into account how surface charge may affect surface energy. It implies that the highest surface energy may occur around the point of zero charge (p.z.c), where the nucleation is fastest (or conversely, where the induction time is shortest) under low saturation states, but not under high saturation states. An accelerated attachment rate of monomers at the p.z.c. is consistent with high surface energy, since it represents higher reactivity of surface ions and less work needed to break the solvated water molecules. This study provides deeper insights into mechanisms of nesquehonite nucleation in nature, and guidelines for accelerating the precipitation rates of nesquehonite.

Effects of brash removal after clear felling on soil and soil-solution chemistry and field-layer biomass in an experimental nitrogen gradient.

PubMed

Ring, E; Högbom, L; Nohrstedt, H O

2001-10-12

Biofuels, such as brash from forest fellings, have been proposed as an alternative energy source. Brash removal may affect the sustainability of forest production, e.g., through a change in the availability of cations and N in the soil. We report initial effects of brash removal on inorganic N content in humus and mineral soil, soil-solution chemistry, and field-layer biomass after clear felling an N-fertilisation experiment in central Sweden. The experiment comprised six different fertiliser levels, ranging from 0 to 600 kg N ha(-1). Urea was given every 5th year during 1967 to 1982 to replicated plots, giving total doses of 0 to 2400 kg N ha(-1). Clear felling took place in 1995, 13 years after the last fertilisation. The removal of brash decreased the NO3- content in the humus layer after clear felling. A decrease in the NO3- concentration of the soil solution was indicated during most of the study period as well. No effect of the previous N fertilisation was found in the humus layer, but in the mineral soil there was an increase in NO3- content for the highest N dose after clear felling ( p = 0.06). The soil-solution chemistry and the field-layer biomass showed an irregular pattern with no consistent effects of brash removal or previous fertilisation.

Use of radiation in preparative chemistry

NASA Technical Reports Server (NTRS)

Philipp, W. H.; Marksik, S. J.; May, C. E.; Lad, R. A.

1971-01-01

A summary and updating of previous work on the use of radiation chemistry for the preparation of pure materials are presented. Work was chiefly concerned with the reduction of metal salts in solution to the free metal using 2 MeV electrons. Metals deposited from aqueous solution are copper, silver, zinc, cadmium, thallium, tin, lead, antimony, iron, nickel, cobalt, and palladium. Dry organic solvents were evaluated for the deposition of metals based on a study involving deposition of antimony from soltions of antimony (III) chloride. The use of organic liquids for the preparation of anhydrous metal halides is also presented. Reaction mechanisms for both organic liquids and aqueous system are discussed.

Characterization of PMR polyimide resin and prepreg

NASA Technical Reports Server (NTRS)

Lindenmeyer, P. H.; Sheppard, C. H.

1984-01-01

Procedures for the chemical characterization of PMR-15 resin solutions and graphite-reinforced prepregs were developed, and a chemical data base was established. In addition, a basic understanding of PMR-15 resin chemistry was gained; this was translated into effective processing procedures for the production of high quality graphite composites. During the program the PMR monomers and selected model compounds representative of postulated PMR-15 solution chemistry were acquired and characterized. Based on these data, a baseline PMR-15 resin was formulated and evaluated for processing characteristics and composite properties. Commercially available PMR-15 resins were then obtained and chemically characterized. Composite panels were fabricated and evaluated.

CAG12 - A CSCM based procedure for flow of an equilibrium chemically reacting gas

NASA Technical Reports Server (NTRS)

Green, M. J.; Davy, W. C.; Lombard, C. K.

1985-01-01

The Conservative Supra Characteristic Method (CSCM), an implicit upwind Navier-Stokes algorithm, is extended to the numerical simulation of flows in chemical equilibrium. The resulting computer code known as Chemistry and Gasdynamics Implicit - Version 2 (CAG12) is described. First-order accurate results are presented for inviscid and viscous Mach 20 flows of air past a hemisphere-cylinder. The solution procedure captures the bow shock in a chemically reacting gas, a technique that is needed for simulating high altitude, rarefied flows. In an initial effort to validate the code, the inviscid results are compared with published gasdynamic and chemistry solutions and satisfactorily agreement is obtained.

Adsorption of aquatic humic substances on colloidal-size aluminum oxide particles: Influence of solution chemistry

NASA Astrophysics Data System (ADS)

Schlautman, Mark A.; Morgan, James J.

1994-10-01

The adsorption of Suwannee River humic substances (HS) on colloidal-size aluminum oxide particles was examined as a function of solution chemistry. The amount of humic acid (HA) or fulvic acid (FA) adsorbed decreased with increasing pH for all solutions of constant ionic strength. In NaCl solutions at fixed pH values, the adsorption of HA and FA increased with increasing ionic strength. The presence of Ca 2+ enhanced the adsorption of HA but had little effect on FA. For identical solution conditions, the amount (by mass) of HA adsorbed to alumina was always greater than FA. Adsorption densities for both HA and FA showed good agreement with the Langmuir equation, and interpretations of adsorption processes were made from the model parameters. For FA, ligand exchange appears to be the dominant adsorption reaction for the conditions studied here. Ligand exchange is also a major adsorption reaction for HA; however, other reactions contribute to adsorption for some solution compositions. At high pH, cation and water bridging become increasingly important for HA adsorption with increasing amounts of Na + and Ca 2+, respectively. At low to neutral pH values, increases in these same two cations make hydrophobic bonding more effective. Calculations of HS carboxyl group densities in the adsorbed layer support the proposed adsorption reactions. From the adsorption data it appears that fewer than 3.3 HS-COO - groups per nm 2 can be bound directly as inner-sphere complexes by the alumina surface. We propose that the influence of aqueous chemistry on HS adsorption reactions, and therefore on the types of HS surface complexes formed, affects the formation and nature of organic coatings on mineral surfaces.

Hydrolysis and Radiation Chemistry of the DGAs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mincher, Bruce Jay; Zarzana, Christopher Andrew

This document was prepared to meet FCR&D level 3 milestone M3FT-16IN030104052, “continue the study of the short chain compounds,” and, “ study the radiolysis of the non-symmetrical DGA (D3DODGA)….,” under the Radiation Chemistry FCR&D work package. Toward these goals, the short chain DGA, tetraethyldiglycolamide (TEDGA) was investigated for its hydrolytic stability in HNO3 solution, with comparisons to the less oxidizing mineral acid HCl. Initial gamma-irradiations were also performed on DGA solutions, to inform a more detailed investigation of several short chain compounds anticipated for FY17. The hydrolytic and radiolysis behavior of TEDGA is of interest for two reasons. First, previousmore » long chain DGA radiolysis was conducted in dodecane solution since the long chain compounds are soluble in that diluent, and new radiation chemistry is expected in the aqueous environment due to reactions with •OH radical. The second reason is that this water-soluble DGA has been proposed for use as a stripping or holdback agent in both European and American fuel cycle scenarios. Therefore, this work was performed in collaboration Forschungszentrum Jülich (FZJ), and the European SACSESS program. Additionally, results are presented here regarding the radiation of chemistry the non-symmetrical DGA didodecyldioctyldiglycolamide (D3DODGA), for comparison to previous work with symmetrical DGAs such as TODGA and TEHDGA. This was also conducted in collaboration with researchers in the SACSESS program.« less

Stable-isotope and solute-chemistry approaches to flow characterization in a forested tropical watershed, Luquillo Mountains, Puerto Rico

USGS Publications Warehouse

Scholl, Martha A.; Shanley, James B.; Murphy, Sheila F.; Willenbring, Jane K; Occhi, Marcie; González, Grizelle

2015-01-01

The prospect of changing climate has led to uncertainty about the resilience of forested mountain watersheds in the tropics. In watersheds where frequent, high rainfall provides ample runoff, we often lack understanding of how the system will respond under conditions of decreased rainfall or drought. Factors that govern water supply, such as recharge rates and groundwater storage capacity, may be poorly quantified. This paper describes 8-year data sets of water stable isotope composition (δ2H and δ18O) of precipitation (4 sites) and a stream (1 site), and four contemporaneous stream sample sets of solute chemistry and isotopes, used to investigate watershed response to precipitation inputs in the 1780-ha Río Mameyes basin in the Luquillo Mountains of northeastern Puerto Rico. Extreme δ2H and δ18O values from low-pressure storm systems and the deuterium excess (d-excess) were useful tracers of watershed response in this tropical system. A hydrograph separation experiment performed in June 2011 yielded different but complementary information from stable isotope and solute chemistry data. The hydrograph separation results indicated that 36% of the storm rain that reached the soil surface left the watershed in a very short time as runoff. Weathering-derived solutes indicated near-stream groundwater was displaced into the stream at the beginning of the event, followed by significant dilution. The more biologically active solutes exhibited a net flushing behavior. The d-excess analysis suggested that streamflow typically has a recent rainfall component (∼25%) with transit time less than the sampling resolution of 7 days, and a more well-mixed groundwater component (∼75%). The contemporaneous stream sample sets showed an overall increase in dissolved solute concentrations with decreasing elevation that may be related to groundwater inputs, different geology, and slope position. A considerable amount of water from rain events runs off as quickflow and bypasses subsurface watershed flowpaths, and better understanding of shallow hillslope and deeper groundwater processes in the watershed will require sub-weekly data and detailed transit time modeling. A combined isotopic and solute chemistry approach can guide further studies to a more comprehensive model of the hydrology, and inform decisions for managing water supply with future changes in climate and land use.

Application of a flux-split algorithm to chemically relaxing, hypervelocity blunt-body flows

NASA Technical Reports Server (NTRS)

Balakrishnan, A.

1987-01-01

Viscous, nonequilibrium, hypervelocity flow fields over two axisymmetric configurations are numerically simulated using a factored, implicit, flux-split algorithm. The governing gas-dynamic and species-continuity equations for laminar flow are presented. The gas-dynamics/nonequilibrium-chemistry coupling procedure is developed as part of the solution procedure and is described in detail. Numerical solutions are presented for hypervelocity flows over a hemisphere and over an axisymmetric aeroassisted orbital transfer vehicle using three different chemistry models. The gas models considered are those for an ideal gas, for a frozen gas, and for chemically relaxing air consisting of five species. The calculated results are compared with existing numerical solutions in the literature along the stagnation line of the hemisphere. The effects of free-stream Reynolds number on the nonequilibrium flow field are discussed.

Green Chemistry Techniques for Gold Nanoparticles Synthesis

NASA Astrophysics Data System (ADS)

Cannavino, Sarah A.; King, Christy A.; Ferrara, Davon W.

Gold nanoparticles (AuNPs) are often utilized in many technological and research applications ranging from the detection of tumors, molecular and biological sensors, and as nanoantennas to probe physical processes. As these applications move from the research laboratory to industrial settings, there is a need to develop efficient and sustainable synthesis techniques. Recent research has shown that several food products and beverages containing polyphenols, a common antioxidant, can be used as reducing agents in the synthesis of AuNPs in solution. In this study, we explore a variety of products to determine which allow for the most reproducible solution of nanoparticles based on the size and shapes of particles present. We analyzed the AuNPs solutions using extinction spectroscopy and atomic force microscopy. We also develop a laboratory activity to introduce introductory chemistry and physics students to AuNP synthesis techniques and analysis.

Multidisciplinary Analysis of a Hypersonic Engine

NASA Technical Reports Server (NTRS)

Stewart, M. E. M.; Suresh, A.; Liou, M. S.; Owen, A. K.; Messitt, D. G.

2002-01-01

This paper describes implementation of a technique used to obtain a high fidelity fluid-thermal-structural solution of a combined cycle engine at its scram design point. Single-discipline simulations are insufficient here since interactions from other disciplines are significant. Using off-the-shelf, validated solvers for the fluid, chemistry, thermal, and structural solutions, this approach couples together their results to obtain consistent solutions.

Expanding the Space of Plausible Solutions in a Medical Tutoring System for Problem-Based Learning

ERIC Educational Resources Information Center

Kazi, Hameedullah; Haddawy, Peter; Suebnukarn, Siriwan

2009-01-01

In well-defined domains such as Physics, Mathematics, and Chemistry, solutions to a posed problem can objectively be classified as correct or incorrect. In ill-defined domains such as medicine, the classification of solutions to a patient problem as correct or incorrect is much more complex. Typical tutoring systems accept only a small set of…

ISSUES RELATED TO SOLUTION CHEMISTRY IN MERCURY SAMPLING IMPINGERS

EPA Science Inventory

Analysis of mercury (Hg) speciation in combustion flue gases is often accomplished in standardized sampling trains in which the sample is passed sequentially through a series of aqueous solutions to capture and separate oxidized Hg (Hg2+) and elemental Hg (Hgo). Such methods incl...

Filtrates and Residues: Ice Cream: Delicious Chemistry.

ERIC Educational Resources Information Center

Martino, James

1983-01-01

An experiment involving preparation of ice cream is conducted after students complete units on solutions, atomic structure, molecular architecture, and bonding. The laboratory gives practical illustration of relation of physical properties to bond type and solution theory developed. Materials needed, procedures used, and questions asked are…

Tested Demonstrations. The Stepwise Reduction of Permanganate in Alkaline Conditions: A Lecture Demonstration.

ERIC Educational Resources Information Center

Ruoff, Peter; Riley, Megan

1987-01-01

Describes a chemistry experiment where an alkaline ice-cold permanganate solution is reduced by adding dropwise a cold diluted hydrogen peroxide solution. Outlines the course of the reduction through the various oxidation states of manganese with their characteristic colors. (TW)

Viscosity and Solvation

ERIC Educational Resources Information Center

Robertson, C. T.

1973-01-01

Discusses theories underlying the phenomena of solution viscosities, involving the Jones and Dole equation, B-coefficient determination, and flickering cluster model. Indicates that viscosity measurements provide a basis for the study of the structural effects of ions in aqueous solutions and are applicable in teaching high school chemistry. (CC)

Multiple solutions in the theory of direct current glow discharges: Effect of plasma chemistry and nonlocality, different plasma-producing gases, and 3D modelling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Almeida, P. G. C.; Benilov, M. S.

2013-10-15

The work is aimed at advancing the multiple steady-state solutions that have been found recently in the theory of direct current (DC) glow discharges. It is shown that an account of detailed plasma chemistry and non-locality of electron transport and kinetic coefficients results in an increase of the number of multiple solutions but does not change their pattern. Multiple solutions are shown to exist for discharges in argon and helium provided that discharge pressure is high enough. This result indicates that self-organization in DC glow microdischarges can be observed not only in xenon, which has been the case until recently,more » but also in other plasma-producing gases; a conclusion that has been confirmed by recent experiments. Existence of secondary bifurcations can explain why patterns of spots grouped in concentric rings, observed in the experiment, possess in many cases higher number of spots in outer rings than in inner ones.« less

Design of Chemistry Teacher Education Course on Nature of Science

NASA Astrophysics Data System (ADS)

Vesterinen, Veli-Matti; Aksela, Maija

2013-09-01

To enhance students' understanding of nature of science (NOS), teachers need adequate pedagogical content knowledge related to NOS. The educational design research study presented here describes the design and development of a pre-service chemistry teacher education course on NOS instruction. The study documents two iterative cycles of problem analysis, design, implementation, and evaluation. The main aims of the study were (1) to create an in-depth and detailed description of the process used in the development of the course and the design solutions produced, and (2) to evaluate how the design solutions affected participants' commitment to teach NOS. Based on the problem analysis based on challenges recognized from the previous research, three design solutions were produced: (1) definition of central dimensions of domain-specific NOS for chemistry education, (2) teaching cycle for explicit and structured opportunities for reflection and discussion, and (3) design assignments to translate NOS understanding into classroom practice. The major data-sources used in the evaluation of the design solutions were the four in-depth interviews conducted after the course. Based on the evaluation, the design solutions supported internalizing understanding of NOS and transforming the understanding to instruction. Supporting the implementation of new innovative teaching practices such as NOS instruction in pre-service teacher education is a challenge. However, the success of the participants in implementing NOS instruction demonstrates, that a pre-service teacher education course can be successful in producing early adopters of NOS instruction and thus might be one of the first steps in injecting NOS instruction into the curriculum.

A Hypermedia Environment To Explore and Negotiate Students' Conceptions: Animation of the Solution Process of Table Salt.

ERIC Educational Resources Information Center

Ebenezer, Jazlin V.

2001-01-01

Describes the characteristics and values of hypermedia for learning chemistry. Reports on how a hypermedia environment was used to explore a group of 11th grade chemistry students' conceptions of table salt dissolving in water. Indicates that a hypermedia environment can be used to explore, negotiate, and assess students' conceptions of…

Determination of Molecular Self-Diffusion Coefficients Using Pulsed-Field-Gradient NMR: An Experiment for Undergraduate Physical Chemistry Laboratory

ERIC Educational Resources Information Center

Harmon, Jennifer; Coffman, Cierra; Villarrial, Spring; Chabolla, Steven; Heisel, Kurt A.; Krishnan, Viswanathan V.

2012-01-01

NMR spectroscopy has become one of the primary tools that chemists utilize to characterize a range of chemical species in the solution phase, from small organic molecules to medium-sized proteins. A discussion of NMR spectroscopy is an essential component of physical and biophysical chemistry lecture courses, and a number of instructional…

Greener "Solutions" for the Organic Chemistry Teaching Lab: Exploring the Advantages of Alternative Reaction Media

ERIC Educational Resources Information Center

McKenzie, Lallie C.; Huffman, Lauren M.; Hutchison, James E.; Rogers, Courtney E.; Goodwin, Thomas E.; Spessard, Gary O.

2009-01-01

A major approach for implementing green chemistry is the discovery and development of synthetic strategies that reduce the quantity of solvent needed, eliminate it altogether, or rely on new reaction media. An increasing number of examples have demonstrated that greener reaction solvents or media can enhance performance as well as reduce hazard.…

Ligand-Free Suzuki-Miyaura Coupling Reactions Using an Inexpensive Aqueous Palladium Source: A Synthetic and Computational Exercise for the Undergraduate Organic Chemistry Laboratory

ERIC Educational Resources Information Center

Hill, Nicholas J.; Bowman, Matthew D.; Esselman, Brian J.; Byron, Stephen D.; Kreitinger, Jordan; Leadbeater, Nicholas E.

2014-01-01

An inexpensive procedure for introducing the Suzuki-Miyaura coupling reaction into a high-enrollment undergraduate organic chemistry laboratory course is described. The procedure employs an aqueous palladium solution as the catalyst and a range of para-substituted aryl bromides and arylboronic acids as substrates. The coupling reactions proceed…

Equilibrium II: Acids and Bases. Independent Learning Project for Advanced Chemistry (ILPAC). Unit P3.

ERIC Educational Resources Information Center

Inner London Education Authority (England).

This unit on equilibrium is one of 10 first year units produced by the Independent Learning Project for Advanced Chemistry (ILPAC). The unit, which consists of two levels, focuses on the application of equilibrium principles to equilibria involving weak acids and bases, including buffer solutions and indicators. Level one uses Le Chatelier's…

Computational Modeling of the Optical Rotation of Amino Acids: An "in Silico" Experiment for Physical Chemistry

ERIC Educational Resources Information Center

Simpson, Scott; Autschbach, Jochen; Zurek, Eva

2013-01-01

A computational experiment that investigates the optical activity of the amino acid valine has been developed for an upper-level undergraduate physical chemistry laboratory course. Hybrid density functional theory calculations were carried out for valine to confirm the rule that adding a strong acid to a solution of an amino acid in the l…

Toward Solutions: The Work of the Chemistry Action-Research Group. Learning in Science Project. Working Paper No. 35.

ERIC Educational Resources Information Center

Osborne, Roger; And Others

In the action-research phase of the Learning in Science Project, four groups of people worked on problems identified in the project's second (in-depth) phase. The Chemistry Action-Research Group considered problems related to the teaching and learning of ideas associated with particles and physical/chemical changes. Based on findings during the…

Computational solution of atmospheric chemistry problems

NASA Technical Reports Server (NTRS)

Jafri, J.; Ake, R. L.

1986-01-01

Extensive studies were performed on problems of interest in atmospheric chemistry. In addition to several minor projects, four major projects were performed and described (theoretical studies of ground and low-lying excited states of ClO2; ground and excited state potential energy surfaces of the methyl peroxy radical; electronic states ot the FO radical; and theoretical studies S02 (H2O) (sub n)).

General Chemistry Students' Conceptual Understanding and Language Fluency: Acid-Base Neutralization and Conductometry

ERIC Educational Resources Information Center

Nyachwaya, James M.

2016-01-01

The objective of this study was to examine college general chemistry students' conceptual understanding and language fluency in the context of the topic of acids and bases. 115 students worked in groups of 2-4 to complete an activity on conductometry, where they were given a scenario in which a titration of sodium hydroxide solution and dilute…

Inactivation of virus in solution by cold atmospheric pressure plasma: identification of chemical inactivation pathways

NASA Astrophysics Data System (ADS)

Aboubakr, Hamada A.; Gangal, Urvashi; Youssef, Mohammed M.; Goyal, Sagar M.; Bruggeman, Peter J.

2016-05-01

Cold atmospheric pressure plasma (CAP) inactivates bacteria and virus through in situ production of reactive oxygen and nitrogen species (RONS). While the bactericidal and virucidal efficiency of plasmas is well established, there is limited knowledge about the chemistry leading to the pathogen inactivation. This article describes a chemical analysis of the CAP reactive chemistry involved in the inactivation of feline calicivirus. We used a remote radio frequency CAP produced in varying gas mixtures leading to different plasma-induced chemistries. A study of the effects of selected scavengers complemented with positive control measurements of relevant RONS reveal two distinctive pathways based on singlet oxygen and peroxynitrous acid. The first mechanism is favored in the presence of oxygen and the second in the presence of air when a significant pH reduction is induced in the solution by the plasma. Additionally, smaller effects of the H2O2, O3 and \\text{NO}2- produced were also found. Identification of singlet oxygen-mediated 2-imidazolone/2-oxo-His (His  +14 Da)—an oxidative modification of His 262 comprising the capsid protein of feline calicivirus links the plasma induced singlet oxygen chemistry to viral inactivation.

Controlled Redox Chemistry at Cerium within a Tripodal Nitroxide Ligand Framework

DOE PAGES

Bogart, Justin A.; Lippincott, Connor A.; Carroll, Patrick J.; ...

2015-10-27

Ligand reorganization has been shown to have a profound effect on the outcome of cerium redox chemistry. Through the use of a tethered, tripodal, trianionic nitroxide ligand, [((2-tBuNOH)C 6 H 4 CH 2 ) 3 N] 3- (TriNO x 3- ), controlled redox chemistry at cerium was accomplished, and typically reactive complexes of tetravalent cerium were isolated. These included rare cationic complexes [Ce(TriNO x )thf][BAr F 4 ], in which Ar F =3,5-(CF 3 ) 2 -C 6 H 3 , and [Ce(TriNO x )py][OTf] . A rare complete Ce-halide series, Ce(TriNO x )X, in which X=F - , Clmore » - , Br - , I - , was also synthesized. We explored the solution chemistry of these complexes through detailed solution-phase electrochemistry and 1 H NMR experiments and showed a unique shift in the ratio of species with inner- and outer-sphere anions with size of the anionic X - group. DFT calculations on the series of calculations corroborated the experimental findings. Also, the use of a bulky and strongly donating tethered tripodal nitroxide ligand allowed the controlled redox chemistry at cerium. As a result, rare examples of cationic Ce IV complexes were synthesized and fully characterized. The full Ce-halide series supported by the tripodal ligand framework is also reported (see scheme).« less

Problems Relating Mathematics and Science in the High School.

ERIC Educational Resources Information Center

Morrow, Richard; Beard, Earl

This document contains various science problems which require a mathematical solution. The problems are arranged under two general areas. The first (algebra I) contains biology, chemistry, and physics problems which require solutions related to linear equations, exponentials, and nonlinear equations. The second (algebra II) contains physics…

Hysteresis of Colloid Retention and Release in Saturated Porous Media During Transients in Solution Chemistry

USDA-ARS?s Scientific Manuscript database

Saturated packed column and micromodel transport studies wereconducted to gain insightonmechanismsof colloid retention and release under unfavorable attachment conditions. The initial deposition of colloids in porous media was found to be a strongly coupled process that depended on solution chemistr...

Adsorption of dyes by ACs prepared from waste tyre reinforcing fibre. Effect of texture, surface chemistry and pH.

PubMed

Acevedo, Beatriz; Rocha, Raquel P; Pereira, Manuel F R; Figueiredo, José L; Barriocanal, Carmen

2015-12-01

This paper compares the importance of the texture and surface chemistry of waste tyre activated carbons in the adsorption of commercial dyes. The adsorption of two commercial dyes, Basic Astrazon Yellow 7GLL and Reactive Rifafix Red 3BN on activated carbons made up of reinforcing fibres from tyre waste and low-rank bituminous coal was studied. The surface chemistry of activated carbons was modified by means of HCl-HNO3 treatment in order to increase the number of functional groups. Moreover, the influence of the pH on the process was also studied, this factor being of great importance due to the amphoteric characteristics of activated carbons. The activated carbons made with reinforcing fibre and coal had the highest SBET, but the reinforcing fibre activated carbon samples had the highest mesopore volume. The texture of the activated carbons was not modified upon acid oxidation treatment, unlike their surface chemistry which underwent considerable modification. The activated carbons made with a mixture of reinforcing fibre and coal experienced the largest degree of oxidation, and so had more acid surface groups. The adsorption of reactive dye was governed by the mesoporous volume, whilst surface chemistry played only a secondary role. However, the surface chemistry of the activated carbons and dispersive interactions played a key role in the adsorption of the basic dye. The adsorption of the reactive dye was more favored in a solution of pH 2, whereas the basic dye was adsorbed more easily in a solution of pH 12. Copyright © 2015 Elsevier Inc. All rights reserved.

Dial-A-Decon Solution Chemistry GAP Testing

DTIC Science & Technology

2012-04-01

34 The tubes were serially diluted using Buttcrfield’s buffer solution and plated in triplicate on Tryptic Soy Agar. Plates were enumerated the...of 200 uL HD to 10 mL of the surfactant solution. The energy to create the oil in water (O/W) emulsions was provided by magnetic stirring. Solutions...emulsify a mixture of water and oil such as HD, one or more emulsifiers are required. Each surfactant system can be characterized by an HLB value

Effects of numerical tolerance levels on an atmospheric chemistry model for mercury

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferris, D.C.; Burns, D.S.; Shuford, J.

1996-12-31

A Box Model was developed to investigate the atmospheric oxidation processes of mercury in the environment. Previous results indicated the most important influences on the atmospheric concentration of HgO(g) are (i) the flux of HgO(g) volatilization, which is related to the surface medium, extent of contamination, and temperature, and (ii) the presence of Cl{sub 2} in the atmosphere. The numerical solver which has been incorporated into the ORganic CHemistry Integrated Dispersion (ORCHID) model uses the Livermore Solver of Ordinary Differential Equations (LSODE). In the solution of the ODE`s, LSODE uses numerical tolerances. The tolerances effect computer run time, the relativemore » accuracy of ODE calculated species concentrations and whether or not LSODE converges to a solution using this system of equations. The effects of varying these tolerances on the solution of the box model and the ORCHID model will be discussed.« less

Development of a Polarizable Force Field for Molecular Dynamics Simulations of Poly (Ethylene Oxide) in Aqueous Solution.

PubMed

Starovoytov, Oleg N; Borodin, Oleg; Bedrov, Dmitry; Smith, Grant D

2011-06-14

We have developed a quantum chemistry-based polarizable potential for poly(ethylene oxide) (PEO) in aqueous solution based on the APPLE&P polarizable ether and the SWM4-DP polarizable water models. Ether-water interactions were parametrized to reproduce the binding energy of water with 1,2-dimethoxyethane (DME) determined from high-level quantum chemistry calculations. Simulations of DME-water and PEO-water solutions at room temperature using the new polarizable potentials yielded thermodynamic properties in good agreement with experimental results. The predicted miscibility of PEO and water as a function of the temperature was found to be strongly correlated with the predicted free energy of solvation of DME. The developed nonbonded force field parameters were found to be transferrable to poly(propylene oxide) (PPO), as confirmed by capturing, at least qualitatively, the miscibility of PPO in water as a function of the molecular weight.

Finite-Difference Solution for Laminar or Turbulent Boundary Layer Flow over Axisymmetric Bodies with Ideal Gas, CF4, or Equilibrium Air Chemistry

NASA Technical Reports Server (NTRS)

Hamilton, H. Harris, II; Millman, Daniel R.; Greendyke, Robert B.

1992-01-01

A computer code was developed that uses an implicit finite-difference technique to solve nonsimilar, axisymmetric boundary layer equations for both laminar and turbulent flow. The code can treat ideal gases, air in chemical equilibrium, and carbon tetrafluoride (CF4), which is a useful gas for hypersonic blunt-body simulations. This is the only known boundary layer code that can treat CF4. Comparisons with experimental data have demonstrated that accurate solutions are obtained. The method should prove useful as an analysis tool for comparing calculations with wind tunnel experiments and for making calculations about flight vehicles where equilibrium air chemistry assumptions are valid.

Finite-difference solution for laminar or turbulent boundary layer flow over axisymmetric bodies with ideal gas, CF4, or equilibrium air chemistry

NASA Astrophysics Data System (ADS)

Hamilton, H. Harris, II; Millman, Daniel R.; Greendyke, Robert B.

1992-12-01

A computer code was developed that uses an implicit finite-difference technique to solve nonsimilar, axisymmetric boundary layer equations for both laminar and turbulent flow. The code can treat ideal gases, air in chemical equilibrium, and carbon tetrafluoride (CF4), which is a useful gas for hypersonic blunt-body simulations. This is the only known boundary layer code that can treat CF4. Comparisons with experimental data have demonstrated that accurate solutions are obtained. The method should prove useful as an analysis tool for comparing calculations with wind tunnel experiments and for making calculations about flight vehicles where equilibrium air chemistry assumptions are valid.

Rare earth metal-containing ionic liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prodius, Denis; Mudring, Anja-Verena

As an innovative tool, ionic liquids (ILs) are widely employed as an alternative, smart, reaction media (vs. traditional solvents) offering interesting technology solutions for dissolving, processing and recycling of metal-containing materials. The costly mining and refining of rare earths (RE), combined with increasing demand for high-tech and energy-related applications around the world, urgently requires effective approaches to improve the efficiency of rare earth separation and recovery. In this context, ionic liquids appear as an attractive technology solution. Finally, this paper addresses the structural and coordination chemistry of ionic liquids comprising rare earth metals with the aim to add to understandingmore » prospects of ionic liquids in the chemistry of rare earths.« less

Rare earth metal-containing ionic liquids

DOE PAGES

Prodius, Denis; Mudring, Anja-Verena

2018-03-07

As an innovative tool, ionic liquids (ILs) are widely employed as an alternative, smart, reaction media (vs. traditional solvents) offering interesting technology solutions for dissolving, processing and recycling of metal-containing materials. The costly mining and refining of rare earths (RE), combined with increasing demand for high-tech and energy-related applications around the world, urgently requires effective approaches to improve the efficiency of rare earth separation and recovery. In this context, ionic liquids appear as an attractive technology solution. Finally, this paper addresses the structural and coordination chemistry of ionic liquids comprising rare earth metals with the aim to add to understandingmore » prospects of ionic liquids in the chemistry of rare earths.« less

Thiolated graphene - a new platform for anchoring CdSe quantum dots for hybrid heterostructures

NASA Astrophysics Data System (ADS)

Debgupta, Joyashish; Pillai, Vijayamohanan K.

2013-04-01

Effective organization of small CdSe quantum dots on graphene sheets has been achieved by a simple solution exchange with thiol terminated graphene prepared by diazonium salt chemistry. This generic methodology of CdSe QD attachment to any graphene surface has remarkable implications in designing hybrid heterostructures.Effective organization of small CdSe quantum dots on graphene sheets has been achieved by a simple solution exchange with thiol terminated graphene prepared by diazonium salt chemistry. This generic methodology of CdSe QD attachment to any graphene surface has remarkable implications in designing hybrid heterostructures. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr00363a

Solution Calorimetry Experiments for Physical Chemistry.

ERIC Educational Resources Information Center

Raizen, Deborah A.; And Others

1988-01-01

Presents two experiments: the first one measures the heat of an exothermic reaction by the reduction of permanganate by the ferris ion; the second one measures the heat of an endothermic process, the mixing of ethanol and cyclohexane. Lists tables to aid in the use of the solution calorimeter. (MVL)

NUMERICAL TECHNIQUES TO SOLVE CONDENSATIONAL AND DISSOLUTIONAL GROWTH EQUATIONS WHEN GROWTH IS COUPLED TO REVERSIBLE REACTIONS (R823186)

EPA Science Inventory

Noniterative, unconditionally stable numerical techniques for solving condensational and
dissolutional growth equations are given. Growth solutions are compared to Gear-code solutions for
three cases when growth is coupled to reversible equilibrium chemistry. In all cases, ...

Dynamic chemistry in the perched groundwater flowing through weathered bedrock underling a steep forested hillslope, north California

NASA Astrophysics Data System (ADS)

Kim, H.; Rempe, D. M.; Bishop, J. K.; Dietrich, W.; Fung, I.; Wood, T. J.

2012-12-01

The spatial and temporal pattern of groundwater chemistry in the seasonally perched groundwater systems that develop in the weathered bedrock zone under hillslopes have rarely been documented, yet chemical evolution of water here dictates the runoff chemistry to streams in many places. Here we exploit an intensively instrumented hillslope to document water well chemistry at three wells and adjacent stream. We have been sampling groundwater at daily frequency since October 2008 on a forested hillslope, "Rivendell", at the Angelo Coast Range Reserve located at the headwaters of the Eel River, California. The site is typical of California's coastal Mediterranean climate. The groundwater samples have been collected from a depth near the boundary between the weathered and fresh bedrock at three locations along the hillslope: Well 1 (bottom of hillslope), Well 3 (mid-slope), and Well 10 (near the ridge). Bulk rainwater and throughfall samples were collected at a meadow across the hillslope and at the middle of the slope, respectively, as well. Near the ridge (Well 10), during the first significant rainstorms of 2009 (133mm/42.5hours) and 2010 (220mm/42hours), when the water table changed only 0.32m and 0.66m, respectively, the concentration of Ca, Mg, and Na started to increase rapidly compared to the dry season (e.g. 2-6 μM vs 0.02-0.2μM [Mg]/day). However, during these same storms, K concentration sharply increased to 50-60 μM and decreased to 20-30μM, synchronizing with the water table responses. Throughfalls of these storms had at least 10 fold lower Ca, Mg, and Na concentrations than the well water while they had 10 fold higher K compared to the pre-event groundwater values. When the total seasonal cumulative rainfall exceeds 600 mm, the Well 10 solute concentration was diluted nearly 3 fold (e.g. [Mg] 0.3 mM vs. 0.1 mM) and the water table was raised significantly (2-6 meters). Throughout the rainy season, Well10 retained its diluted chemistry signature and on average the water table remained elevated as subsequent rainstorms repeatedly recharged the system. Well10 solute concentration slowly increased at the end of the rainy season when the water table fell. In contrast, at the foot of the hill slope, even though the water table was responsive to each rainfall event, its water chemistry developed a strong dilution signatures only during the intense rainstorms (total rainfall > 70mm); the solute concentration decreased (e.g. [Mg] = 0.1mM) during the rising limb of the well hydrograph and recovered back to its pre-event value (e.g. [Mg] = 0.3mM) during the falling limb of the well hydrograph. During small storms, the solute concentration of Well 1 either did not change or slightly increased. Mid-slope showed similar behavior to Well 1. The Well 3 solute concentration was diluted about 3 fold (e.g. [Mg] 0.3mM to 0.1mM) as the water table rose and increased as the water table receded. However unlike Well 1, the water chemistry of Well 3 did not recover to its pre-event composition at any point during the rainy season and the recovery rate was slower than that of Well 1. These water chemistry observations provide insight into the dynamics of water movement within the fractured, weathered bedrock zone, and point to both vertical and lateral mixing processes that influence the chemical evolution of waters.

Tuning colloidal quantum dot band edge positions through solution-phase surface chemistry modification

DOE PAGES

Kroupa, Daniel M.; Vörös, Márton; Brawand, Nicholas P.; ...

2017-05-16

Band edge positions of semiconductors determine their functionality in many optoelectronic applications such as photovoltaics, photoelectrochemical cells and light emitting diodes. Here we show that band edge positions of lead sulfide (PbS) colloidal semiconductor nanocrystals, specifically quantum dots (QDs), can be tuned over 2.0 eV through surface chemistry modification. We achieved this remarkable control through the development of simple, robust and scalable solution-phase ligand exchange methods, which completely replace native ligands with functionalized cinnamate ligands, allowing for well-defined, highly tunable chemical systems. By combining experiments and ab initio simulations, we establish clear relationships between QD surface chemistry and the bandmore » edge positions of ligand/QD hybrid systems. We find that in addition to ligand dipole, inter-QD ligand shell inter-digitization contributes to the band edge shifts. As a result, we expect that our established relationships and principles can help guide future optimization of functional organic/inorganic hybrid nanostructures for diverse optoelectronic applications.« less

Tuning colloidal quantum dot band edge positions through solution-phase surface chemistry modification

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kroupa, Daniel M.; Vörös, Márton; Brawand, Nicholas P.

Band edge positions of semiconductors determine their functionality in many optoelectronic applications such as photovoltaics, photoelectrochemical cells and light emitting diodes. Here we show that band edge positions of lead sulfide (PbS) colloidal semiconductor nanocrystals, specifically quantum dots (QDs), can be tuned over 2.0 eV through surface chemistry modification. We achieved this remarkable control through the development of simple, robust and scalable solution-phase ligand exchange methods, which completely replace native ligands with functionalized cinnamate ligands, allowing for well-defined, highly tunable chemical systems. By combining experiments and ab initio simulations, we establish clear relationships between QD surface chemistry and the bandmore » edge positions of ligand/QD hybrid systems. We find that in addition to ligand dipole, inter-QD ligand shell inter-digitization contributes to the band edge shifts. As a result, we expect that our established relationships and principles can help guide future optimization of functional organic/inorganic hybrid nanostructures for diverse optoelectronic applications.« less

Tuning colloidal quantum dot band edge positions through solution-phase surface chemistry modification

PubMed Central

Kroupa, Daniel M.; Vörös, Márton; Brawand, Nicholas P.; McNichols, Brett W.; Miller, Elisa M.; Gu, Jing; Nozik, Arthur J.; Sellinger, Alan; Galli, Giulia; Beard, Matthew C.

2017-01-01

Band edge positions of semiconductors determine their functionality in many optoelectronic applications such as photovoltaics, photoelectrochemical cells and light emitting diodes. Here we show that band edge positions of lead sulfide (PbS) colloidal semiconductor nanocrystals, specifically quantum dots (QDs), can be tuned over 2.0 eV through surface chemistry modification. We achieved this remarkable control through the development of simple, robust and scalable solution-phase ligand exchange methods, which completely replace native ligands with functionalized cinnamate ligands, allowing for well-defined, highly tunable chemical systems. By combining experiments and ab initio simulations, we establish clear relationships between QD surface chemistry and the band edge positions of ligand/QD hybrid systems. We find that in addition to ligand dipole, inter-QD ligand shell inter-digitization contributes to the band edge shifts. We expect that our established relationships and principles can help guide future optimization of functional organic/inorganic hybrid nanostructures for diverse optoelectronic applications. PMID:28508866

Tuning colloidal quantum dot band edge positions through solution-phase surface chemistry modification

NASA Astrophysics Data System (ADS)

Kroupa, Daniel M.; Vörös, Márton; Brawand, Nicholas P.; McNichols, Brett W.; Miller, Elisa M.; Gu, Jing; Nozik, Arthur J.; Sellinger, Alan; Galli, Giulia; Beard, Matthew C.

2017-05-01

Band edge positions of semiconductors determine their functionality in many optoelectronic applications such as photovoltaics, photoelectrochemical cells and light emitting diodes. Here we show that band edge positions of lead sulfide (PbS) colloidal semiconductor nanocrystals, specifically quantum dots (QDs), can be tuned over 2.0 eV through surface chemistry modification. We achieved this remarkable control through the development of simple, robust and scalable solution-phase ligand exchange methods, which completely replace native ligands with functionalized cinnamate ligands, allowing for well-defined, highly tunable chemical systems. By combining experiments and ab initio simulations, we establish clear relationships between QD surface chemistry and the band edge positions of ligand/QD hybrid systems. We find that in addition to ligand dipole, inter-QD ligand shell inter-digitization contributes to the band edge shifts. We expect that our established relationships and principles can help guide future optimization of functional organic/inorganic hybrid nanostructures for diverse optoelectronic applications.

Modelling Detailed-Chemistry Effects on Turbulent Diffusion Flames using a Parallel Solution-Adaptive Scheme

NASA Astrophysics Data System (ADS)

Jha, Pradeep Kumar

Capturing the effects of detailed-chemistry on turbulent combustion processes is a central challenge faced by the numerical combustion community. However, the inherent complexity and non-linear nature of both turbulence and chemistry require that combustion models rely heavily on engineering approximations to remain computationally tractable. This thesis proposes a computationally efficient algorithm for modelling detailed-chemistry effects in turbulent diffusion flames and numerically predicting the associated flame properties. The cornerstone of this combustion modelling tool is the use of parallel Adaptive Mesh Refinement (AMR) scheme with the recently proposed Flame Prolongation of Intrinsic low-dimensional manifold (FPI) tabulated-chemistry approach for modelling complex chemistry. The effect of turbulence on the mean chemistry is incorporated using a Presumed Conditional Moment (PCM) approach based on a beta-probability density function (PDF). The two-equation k-w turbulence model is used for modelling the effects of the unresolved turbulence on the mean flow field. The finite-rate of methane-air combustion is represented here by using the GRI-Mech 3.0 scheme. This detailed mechanism is used to build the FPI tables. A state of the art numerical scheme based on a parallel block-based solution-adaptive algorithm has been developed to solve the Favre-averaged Navier-Stokes (FANS) and other governing partial-differential equations using a second-order accurate, fully-coupled finite-volume formulation on body-fitted, multi-block, quadrilateral/hexahedral mesh for two-dimensional and three-dimensional flow geometries, respectively. A standard fourth-order Runge-Kutta time-marching scheme is used for time-accurate temporal discretizations. Numerical predictions of three different diffusion flames configurations are considered in the present work: a laminar counter-flow flame; a laminar co-flow diffusion flame; and a Sydney bluff-body turbulent reacting flow. Comparisons are made between the predicted results of the present FPI scheme and Steady Laminar Flamelet Model (SLFM) approach for diffusion flames. The effects of grid resolution on the predicted overall flame solutions are also assessed. Other non-reacting flows have also been considered to further validate other aspects of the numerical scheme. The present schemes predict results which are in good agreement with published experimental results and reduces the computational cost involved in modelling turbulent diffusion flames significantly, both in terms of storage and processing time.

Chemically active colloids near osmotic-responsive walls with surface-chemistry gradients

NASA Astrophysics Data System (ADS)

Popescu, M. N.; Uspal, W. E.; Dietrich, S.

2017-04-01

Chemically active colloids move by creating gradients in the composition of the surrounding solution and by exploiting the differences in their interactions with the various molecular species in solution. If such particles move near boundaries, e.g. the walls of the container confining the suspension, gradients in the composition of the solution are also created along the wall. This give rise to chemi-osmosis (via the interactions of the wall with the molecular species forming the solution), which drives flows coupling back to the colloid and thus influences its motility. Employing an approximate ‘point-particle’ analysis, we show analytically that—owing to this kind of induced active response (chemi-osmosis) of the wall—such chemically active colloids can align with, and follow, gradients in the surface chemistry of the wall. In this sense, these artificial ‘swimmers’ exhibit a primitive form of thigmotaxis with the meaning of sensing the proximity of a (not necessarily discontinuous) physical change in the environment. We show that the alignment with the surface-chemistry gradient is generic for chemically active colloids as long as they exhibit motility in an unbounded fluid, i.e. this phenomenon does not depend on the exact details of the propulsion mechanism. The results are discussed in the context of simple models of chemical activity, corresponding to Janus particles with ‘source’ chemical reactions on one half of the surface and either ‘inert’ or ‘sink’ reactions over the other half.

Determination of lipid bilayer affinities and solvation characteristics by electrokinetic chromatography using polymer-bound lipid bilayer nanodiscs.

PubMed

Penny, William M; Palmer, Christopher P

2018-03-01

Styrene-maleic acid polymer-bound lipid bilayer nanodiscs have been investigated and characterized by electrokinetic chromatography. Linear solvation energy relationship analysis was employed to characterize the changes in solvation environment of nanodiscs of varied belt to lipid ratio, belt polymer chemistry and molecular weight, and lipid composition. Increases in the lipid to belt polymer ratio resulted in smaller, more cohesive nanodiscs with greater electrophoretic mobility. Nanodisc structures with belt polymers of different chemistry and molecular weight were compared and showed only minor changes in solvent characteristics and selectivity consistent with changes in structure of the lipid bilayer. Seven phospholipid and sphingomyelin nanodiscs of different lipid composition were characterized. Changes in lipid head group structure had a significant effect on bilayer-solute interactions. In most cases, changes in alkyl tail structure had no discernible effect on solvation environment aside from those explained by changes in the gel-liquid transition temperature. Comparison to vesicles of similar lipid composition show only minor differences in solvation environment, likely due to differences in lipid composition and bilayer curvature. Together these results provide evidence that the dominant solute-nanodisc interactions are with the lipid bilayer and that head group chemistry has a greater impact on bilayer-solute interactions than alkyl tail or belt polymer structure. Nanodisc electrokinetic chromatography is demonstrated to allow characterization of solute interactions with lipid bilayers of varied composition. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dynamic vertical profiles of peat porewater chemistry in a northern peatland

Treesearch

Natalie A. Griffiths; Stephen D. Sebestyen

2016-01-01

We measured pH, cations, nutrients, and total organic carbon (TOC) over 3 years to examine weekly to monthly variability in porewater chemistry depth profiles (0–3.0 m) in an ombrotrophic bog in Minnesota, USA. We also compared temporal variation at one location to spatial variation in depth profiles at 16 locations across the bog. Most solutes exhibited large...

Measurement of Henry's Law Constants Using Internal Standards: A Quantitative GC Experiment for the Instrumental Analysis or Environmental Chemistry Laboratory

ERIC Educational Resources Information Center

Ji, Chang; Boisvert, Susanne M.; Arida, Ann-Marie C.; Day, Shannon E.

2008-01-01

An internal standard method applicable to undergraduate instrumental analysis or environmental chemistry laboratory has been designed and tested to determine the Henry's law constants for a series of alkyl nitriles. In this method, a mixture of the analytes and an internal standard is prepared and used to make a standard solution (organic solvent)…

A Simple Laboratory Experiment to Determine the Kinetics of Mutarotation of D-Glucose Using a Blood Glucose Meter

ERIC Educational Resources Information Center

Perles, Carlos E.; Volpe, Pedro L. O.

2008-01-01

A simple commercial blood glucose meter is used to follow the kinetics of mutarotation of D-glucose in aqueous solution. The results may be compared with those obtained using an automatic polarimeter, if this is available This experiment is proposed for use by students in a general chemistry, biology, organic chemistry, and physical chemistry…

TDPAC and β-NMR applications in chemistry and biochemistry

NASA Astrophysics Data System (ADS)

Jancso, Attila; Correia, Joao G.; Gottberg, Alexander; Schell, Juliana; Stachura, Monika; Szunyogh, Dániel; Pallada, Stavroula; Lupascu, Doru C.; Kowalska, Magdalena; Hemmingsen, Lars

2017-06-01

Time differential perturbed angular correlation (TDPAC) of γ-rays spectroscopy has been applied in chemistry and biochemistry for decades. Herein we aim to present a comprehensive review of chemical and biochemical applications of TDPAC spectroscopy conducted at ISOLDE over the past 15 years, including elucidation of metal site structure and dynamics in proteins and model systems. β-NMR spectroscopy is well established in nuclear physics, solid state physics, and materials science, but only a limited number of applications in chemistry have appeared. Current endeavors at ISOLDE advancing applications of β-NMR towards chemistry and biochemistry are presented, including the first experiment on 31Mg2+ in an ionic liquid solution. Both techniques require the production of radioisotopes combined with advanced spectroscopic instrumentation present at ISOLDE.

Gas Hydrate Stability at Low Temperatures and High Pressures with Applications to Mars and Europa

NASA Technical Reports Server (NTRS)

Marion, G. M.; Kargel, J. S.; Catling, D. C.

2004-01-01

Gas hydrates are implicated in the geochemical evolution of both Mars and Europa [1- 3]. Most models developed for gas hydrate chemistry are based on the statistical thermodynamic model of van der Waals and Platteeuw [4] with subsequent modifications [5-8]. None of these models are, however, state-of-the-art with respect to gas hydrate/electrolyte interactions, which is particularly important for planetary applications where solution chemistry may be very different from terrestrial seawater. The objectives of this work were to add gas (carbon dioxide and methane) hydrate chemistries into an electrolyte model parameterized for low temperatures and high pressures (the FREZCHEM model) and use the model to examine controls on gas hydrate chemistries for Mars and Europa.

Effects of feed solution chemistry on low pressure reverse osmosis filtration of cesium and strontium.

PubMed

Ding, Shiyuan; Yang, Yu; Huang, Haiou; Liu, Hengchen; Hou, Li-an

2015-08-30

The objective of this study was to identify the removal mechanisms of radionuclides by reverse osmosis (RO) membranes under conditions relevant to full-scale water treatment. For this purpose, the effects of feed solution chemistry on the removal of Cs and Sr by a low pressure RO system was investigated by systematically varying membrane surface charge, ionic composition, and organic matter concentrations. The results showed that the effects of solution chemistry on the filtration of Cs and Sr were related to their hydrated ionic radius, resulting in the predominance of the Donnan's effect and electrostatic interactions, respectively. Consequently, the rejection of Cs increased more pronouncedly than Sr with the increases of feed concentration. Due to the Donnan's effect, different anions decreased the rejection of Cs to different extents in accordance to the order of anions' radii as SO4(2-)>Cl(-)>NO3(-)>F(-). The variations in Sr rejection were influenced by the electrostatic interactions between Sr(2+) and the membrane. In addition, humic acid (HA) lowered the rejection of Cs and caused significant membrane flux decline, but did not change the rejection of Sr. Sr also aggravated HA fouling of the membrane. Copyright © 2015 Elsevier B.V. All rights reserved.

Polymer Chemistry

NASA Technical Reports Server (NTRS)

Williams, Martha; Roberson, Luke; Caraccio, Anne

2010-01-01

This viewgraph presentation describes new technologies in polymer and material chemistry that benefits NASA programs and missions. The topics include: 1) What are Polymers?; 2) History of Polymer Chemistry; 3) Composites/Materials Development at KSC; 4) Why Wiring; 5) Next Generation Wiring Materials; 6) Wire System Materials and Integration; 7) Self-Healing Wire Repair; 8) Smart Wiring Summary; 9) Fire and Polymers; 10) Aerogel Technology; 11) Aerogel Composites; 12) Aerogels for Oil Remediation; 13) KSC's Solution; 14) Chemochromic Hydrogen Sensors; 15) STS-130 and 131 Operations; 16) HyperPigment; 17) Antimicrobial Materials; 18) Conductive Inks Formulations for Multiple Applications; and 19) Testing and Processing Equipment.

The lanthanide contraction beyond coordination chemistry

DOE PAGES

Ferru, Geoffroy; Reinhart, Benjamin; Bera, Mrinal K.; ...

2016-04-06

Lanthanide chemistry is dominated by the ‘lanthanide contraction’, which is conceptualized traditionally through coordination chemistry. Here we break this mold, presenting evidence that the lanthanide contraction manifests outside of the coordination sphere, influencing weak interactions between groups of molecules that drive mesoscale-assembly and emergent behavior in an amphiphile solution. Furthermore, changes in these weak interactions correlate with differences in lanthanide ion transport properties, suggesting new forces to leverage rare earth separation and refining. Our results show that the lanthanide contraction paradigm extends beyond the coordination sphere, influencing structure and properties usually associated with soft matter science.

The lanthanide contraction beyond coordination chemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferru, Geoffroy; Reinhart, Benjamin; Bera, Mrinal K.

Lanthanide chemistry is dominated by the ‘lanthanide contraction’, which is conceptualized traditionally through coordination chemistry. Here we break this mold, presenting evidence that the lanthanide contraction manifests outside of the coordination sphere, influencing weak interactions between groups of molecules that drive mesoscale-assembly and emergent behavior in an amphiphile solution. Furthermore, changes in these weak interactions correlate with differences in lanthanide ion transport properties, suggesting new forces to leverage rare earth separation and refining. Our results show that the lanthanide contraction paradigm extends beyond the coordination sphere, influencing structure and properties usually associated with soft matter science.

Parallel medicinal chemistry approaches to selective HDAC1/HDAC2 inhibitor (SHI-1:2) optimization.

PubMed

Kattar, Solomon D; Surdi, Laura M; Zabierek, Anna; Methot, Joey L; Middleton, Richard E; Hughes, Bethany; Szewczak, Alexander A; Dahlberg, William K; Kral, Astrid M; Ozerova, Nicole; Fleming, Judith C; Wang, Hongmei; Secrist, Paul; Harsch, Andreas; Hamill, Julie E; Cruz, Jonathan C; Kenific, Candia M; Chenard, Melissa; Miller, Thomas A; Berk, Scott C; Tempest, Paul

2009-02-15

The successful application of both solid and solution phase library synthesis, combined with tight integration into the medicinal chemistry effort, resulted in the efficient optimization of a novel structural series of selective HDAC1/HDAC2 inhibitors by the MRL-Boston Parallel Medicinal Chemistry group. An initial lead from a small parallel library was found to be potent and selective in biochemical assays. Advanced compounds were the culmination of iterative library design and possess excellent biochemical and cellular potency, as well as acceptable PK and efficacy in animal models.

Multiple steady states in atmospheric chemistry

NASA Technical Reports Server (NTRS)

Stewart, Richard W.

1993-01-01

The equations describing the distributions and concentrations of trace species are nonlinear and may thus possess more than one solution. This paper develops methods for searching for multiple physical solutions to chemical continuity equations and applies these to subsets of equations describing tropospheric chemistry. The calculations are carried out with a box model and use two basic strategies. The first strategy is a 'search' method. This involves fixing model parameters at specified values, choosing a wide range of initial guesses at a solution, and using a Newton-Raphson technique to determine if different initial points converge to different solutions. The second strategy involves a set of techniques known as homotopy methods. These do not require an initial guess, are globally convergent, and are guaranteed, in principle, to find all solutions of the continuity equations. The first method is efficient but essentially 'hit or miss' in the sense that it cannot guarantee that all solutions which may exist will be found. The second method is computationally burdensome but can, in principle, determine all the solutions of a photochemical system. Multiple solutions have been found for models that contain a basic complement of photochemical reactions involving O(x), HO(x), NO(x), and CH4. In the present calculations, transitions occur between stable branches of a multiple solution set as a control parameter is varied. These transitions are manifestations of hysteresis phenomena in the photochemical system and may be triggered by increasing the NO flux or decreasing the CH4 flux from current mean tropospheric levels.

Vapor Corrosion Response of Low Carbon Steel Exposed to Simulated High Level Radioactive Waste

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wiersma, B

2006-01-26

A program to resolve the issues associated with potential vapor space corrosion and liquid/air interface corrosion in the Type III high level waste tanks is in place. The objective of the program is to develop understanding of vapor space (VSC) and liquid/air interface (LAIC) corrosion to ensure a defensible technical basis to provide accurate corrosion evaluations with regard to vapor space and liquid/air interface corrosion. The results of the FY05 experiments are presented here. The experiments are an extension of the previous research on the corrosion of tank steel exposed to simple solutions to corrosion of the steel when exposedmore » to complex high level waste simulants. The testing suggested that decanting and the consequent residual species on the tank wall is the predominant source of surface chemistry on the tank wall. The laboratory testing has shown that at the boundary conditions of the chemistry control program for solutions greater than 1M NaNO{sub 3}{sup -}. Minor and isolated pitting is possible within crevices in the vapor space of the tanks that contain stagnant dilute solution for an extended period of time, specifically when residues are left on the tank wall during decanting. Liquid/air interfacial corrosion is possible in dilute stagnant solutions, particularly with high concentrations of chloride. The experimental results indicate that Tank 50 would be most susceptible to the potential for liquid/air interfacial corrosion or vapor space corrosion, with Tank 49 and 41 following, since these tanks are nearest to the chemistry control boundary conditions. The testing continues to show that the combination of well-inhibited solutions and mill-scale sufficiently protect against pitting in the Type III tanks.« less

Transient hydrogeological controls on the chemistry of a seepage lake

USGS Publications Warehouse

Krabbenhoft, David P.; Webster, Katherine E.

1995-01-01

A solute mass balance method was used to estimate groundwater inflow and outflow rates for Nevins Lake, Michigan, a seepage lake in the upper peninsula that historically has shown extremely variable water chemistry compared with most other seepage lakes. A 4-year study (1989–1992) of the hydrology and geochemistry of Nevins Lake and its contiguous groundwater system revealed that changes in the mass of dissolved solutes are the result of annual hydraulic gradient reversals. A pronounced acidification of Nevins Lake from 1986 to 1988 was likely caused by drought-induced diminished groundwater inflow rates. In this study, dissolved calcium (the major cation in water of Nevins Lake, groundwater, and precipitation) was used for estimating mass flow rates. During the 1989–1992 period, Nevins Lake showed a reproducible annual cycle in calcium mass. Immediately following spring snowmelt and the resulting hydraulic gradient reversal, the mass of dissolved calcium in the lake increases rapidly, and then it decreases steadily throughout the summer and early fall, at which time the lake becomes hydraulically mounded and receives no groundwater inflow. Groundwater flow rates estimated by the solute mass balance method are sensitive to assumed solute concentrations in discharging groundwater. Pore water samples from the lake bed are shown to be more representative of water discharging to the lake than are samples from piezometers near the lake shore, but spatial and temporal variability in pore water chemistry must be considered. Stable isotope analyses (18O and 2H) of lake water, groundwater, and pore water samples show that water discharging to Nevins Lake in the spring is entirely recycled lake water, and no groundwater derived from terrestrial recharge reaches the lake. The conceptual model formulated during this study linking lake chemistry and the contiguous groundwater system and general groundwater flow patterns surrounding highly transient lake systems are likely transferable to other similar systems.

Special Advanced Studies for Pollution Prevention. Delivery Order 0058: The Monitor - Spring 2000

DTIC Science & Technology

2001-04-01

Process complexity ➨ Strippability ➨ Maturity ➨ Process type and chemistry ➨ Licensing requirements ➨ Vendor information ➨ Niplate 700 (Surface...Courses of Action 4 Identify & Evaluate Potential Alternatives 5 Select Best Alternative & Develop Project 6 Prioritize Projects by Commodity 7 Rank...Burden CS Priority Process Specific P2 OASolution Selection Solution Planning Solution Implementation Solution Evaluation Phase 2 Phase 3 Phase 1

Effect of wood ash application on soil solution chemistry of tropical acid soils: incubation study.

PubMed

Nkana, J C Voundi; Demeyer, A; Verloo, M G

2002-12-01

The objective of this study was to determine the effect of wood ash application on soil solution composition of three tropical acid soils. Calcium carbonate was used as a reference amendment. Amended soils and control were incubated for 60 days. To assess soluble nutrients, saturation extracts were analysed at 15 days intervals. Wood ash application affects the soil solution chemistry in two ways, as a liming agent and as a supplier of nutrients. As a liming agent, wood ash application induced increases in soil solution pH, Ca, Mg, inorganic C, SO4 and DOC. As a supplier of elements, the increase in the soil solution pH was partly due to ligand exchange between wood ash SO4 and OH- ions. Large increases in concentrations of inorganic C, SO4, Ca and Mg with wood ash relative to lime and especially increases in K reflected the supply of these elements by wood ash. Wood ash application could represent increased availability of nutrients for the plant. However, large concentrations of basic cations, SO4 and NO3 obtained with higher application rates could be a concern because of potential solute transport to surface waters and groundwater. Wood ash must be applied at reasonable rates to avoid any risk for the environment.

The behavior of MC3T3-E1 cells on chitosan/poly-L-lysine composite films: effect of nanotopography, surface chemistry, and wettability.

PubMed

Zheng, Zhenhuan; Zhang, Ling; Kong, Lijun; Wang, Aijun; Gong, Yandao; Zhang, Xiufang

2009-05-01

In the present work, a series of composite films were produced from chitosan/poly-L-lysine blend solutions. The surface topography, chemistry, and wettability of composite films were characterized by atomic force microscopy (AFM), attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, and contact angle assay, respectively. For all composite films, blending with poly-L-lysine induced changes in surface chemistry and wettability. Interestingly, it was also found that increasing poly-L-lysine weight fraction in blend solutions could result in different nanoscaled surface topographic features, which displayed particle-, granule-, or fiber-dominant morphologies. MC3T3-E1 osteoblast-like cells were cultured on all composite films to evaluate the effects of surface nanotopography, chemistry, and wettability on cell behavior. The observations indicated that MC3T3-E1 cell behavior was affected by surface topography, chemistry, and wettability simultaneously and that cells showed strong responses to surface topography. On fiber-dominant surface, cells fully spread with obvious cytoskeleton organization and exhibited significantly higher level of adhesion and proliferation compared with particle- or granule-dominant surfaces. Furthermore, fiber-dominant surface also induced greater expression of mature osteogenic marker osteocalcin and higher mineralization based on RT-PCR and von Kossa staining. The results suggest that topographic modification of chitosan substratum at the nanoscale may be exploited in regulating cell behavior for its applications in tissue engineering.

Chemistry of through-fall and stem-flow leachate following rainfall simulation over pinyon and juniper

USDA-ARS?s Scientific Manuscript database

We hypothesized that leachate from pinyon and juniper canopies, following rainfall events, may contribute sizable levels of solutes and C to the soil surface. We quantified solutes and dissolved carbon in stem-flow (SF) and through-fall (TF) following replicated rainfall simulation events in a pinyo...

Henry Taube and Coordination Chemistry

Science.gov Websites

Shifts Caused by Cr++ in Aqueous Solutions, DOE Technical Report, 1962 Reactions of Solvated Ions Final Report, DOE Technical Report, 1962 Isotopic Discrimination of Some Solutes in Liquid Ammonia, DOE Technical Report, 1966 Final Technical Report of Research, DOE Technical Report, 1972 Top Additional Web

A Pollutant Transformation Laboratory Exercise for Environmental Chemistry: The Reduction of Nitrobenzenes by Anaerobic Solutions of Humic Acid

ERIC Educational Resources Information Center

Dunnivant, Frank M.; Reynolds, Mark-Cody

2007-01-01

The laboratory experiment, which acts as a capstone, integrated lecture-laboratory exercise involving solution preparation, pH buffers, [E[subscript]H] (reduction potential) buffers, organic reaction mechanisms, reaction kinetics, and instrumental analysis is presented. The students completing the lecture and laboratory exercises could gain a…

Crystal-chemistry insight into the photocatalytic activity of BiOCl x Br1- x nanoplate solid solutions

NASA Astrophysics Data System (ADS)

Xu, Huan-Yan; Han, Xu; Tan, Qu; Wu, Ke-Jia; Qi, Shu-Yan

2017-06-01

In this study, a facile alcoholysis method was developed to synthesize BiOCl x Br1- x nanoplates at room temperature and atmospheric pressure. In this route, strong acid or alkaline environment was absolutely avoided to realize the high exposure of {001} crystal facets. The regular changes in XRD peaks and cell parameters as a function of the Br content strongly declared that the obtained BiOCl x Br1- x products belonged to a group of solid solutions. The 2D nanosheets with in-plane wrinkles were clearly observed in TEM images. Interestingly, as the Br content increased, band gaps of BiOCl x Br1- x solid solutions gradually decreased. The photocatalytic degradation of RhB under simulated sunlight irradiation indicated that BiOCl0.5Br0.5 had the best photocatalytic activity. From the viewpoint of crystal chemistry, the photocatalytic activity of BiOCl x Br1- x solid solutions was closely related with the exposure amount of {001} facets, interlayer spacing of (001) plane and energy-level position of valence band.

Soluto-inertial phenomena: Designing long-range, long-lasting, surface-specific interactions in suspensions

PubMed Central

Banerjee, Anirudha; Williams, Ian; Azevedo, Rodrigo Nery; Squires, Todd M.

2016-01-01

Equilibrium interactions between particles in aqueous suspensions are limited to distances less than 1 μm. Here, we describe a versatile concept to design and engineer nonequilibrium interactions whose magnitude and direction depends on the surface chemistry of the suspended particles, and whose range may extend over hundreds of microns and last thousands of seconds. The mechanism described here relies on diffusiophoresis, in which suspended particles migrate in response to gradients in solution. Three ingredients are involved: a soluto-inertial “beacon” designed to emit a steady flux of solute over long time scales; suspended particles that migrate in response to the solute flux; and the solute itself, which mediates the interaction. We demonstrate soluto-inertial interactions that extend for nearly half a millimeter and last for tens of minutes, and which are attractive or repulsive, depending on the surface chemistry of the suspended particles. Experiments agree quantitatively with scaling arguments and numerical computations, confirming the basic phenomenon, revealing design strategies, and suggesting a broad set of new possibilities for the manipulation and control of suspended particles. PMID:27410044

High-speed reacting flow simulation using USA-series codes

NASA Astrophysics Data System (ADS)

Chakravarthy, S. R.; Palaniswamy, S.

In this paper, the finite-rate chemistry (FRC) formulation for the USA-series of codes and three sets of validations are presented. USA-series computational fluid dynamics (CFD) codes are based on Unified Solution Algorithms including explicity and implicit formulations, factorization and relaxation approaches, time marching and space marching methodolgies, etc., in order to be able to solve a very wide class of CDF problems using a single framework. Euler or Navier-Stokes equations are solved using a finite-volume treatment with upwind Total Variation Diminishing discretization for the inviscid terms. Perfect and real gas options are available including equilibrium and nonequilibrium chemistry. This capability has been widely used to study various problems including Space Shuttle exhaust plumes, National Aerospace Plane (NASP) designs, etc. (1) Numerical solutions are presented showing the full range of possible solutions to steady detonation wave problems. (2) Comparison between the solution obtained by the USA code and Generalized Kinetics Analysis Program (GKAP) is shown for supersonic combustion in a duct. (3) Simulation of combustion in a supersonic shear layer is shown to have reasonable agreement with experimental observations.

The Thermochemical and Kinetic Properties of Ascorbate are Tuned by its Local Environment: Solution Chemistry and Biochemical Implications

PubMed Central

Warren, Jeffrey J.; Mayer, James M.

2010-01-01

Ascorbate (Vitamin C) is a ubiquitous biological cofactor. While its aqueous solution chemistry has long been studied, many in vivo reactions of ascorbate occur in enzyme active sites or at membrane interfaces, which have varying local environments. This report shows that the rate and driving force of oxidations of two ascorbate derivatives by the TEMPO radical (2,2′-6,6′-tetramethylpiperidine-1-oxyl) in acetonitrile are very sensitive to the presence of various additives. These reactions proceed by the transfer of a proton and an electron (a hydrogen atom), as is typical of biological ascorbate reactions. The measured rate and equilibrium constants vary substantially with added water or other polar solutes in acetonitrile solutions, indicating large shifts in the reducing power of ascorbate. The correlation of rate and equilibrium constants indicates that this effect has a thermochemical origin rather than being a purely kinetic effect. This contrasts with previous examples of solvent effects on hydrogen atom transfer reactions. Potential biological implications of this apparently unique effect are discussed. PMID:20476757

Modification of the Selectivity Properties of Tubular Ceramic Membranes after Alkaline Treatment

PubMed Central

Dutournié, Patrick; Limousy, Lionel; Anquetil, Jérôme

2017-01-01

This work focuses on the selectivity modification of ceramic membranes after a mild alkaline treatment. Filtration of pure salt-water solutions was carried out with commercial titania membranes before and after the treatment. After treatment, the rejection of NaF significantly decreased, while the rejection of NaCl and NaBr increased. Additionally, NaI and Na2SO4 remained close to zero. Pore size and electrical charge being almost unchanged, only significant modifications in the dielectric effects can explain this modification of selectivity. Therefore, the surface chemistry and the interaction (nature and magnitude) with the solvent and with the species present in the solution appear to be modified by the alkaline treatment. This trend is also illustrated by discussing the electric and the dielectric properties that were numerically identified before and after treatment. The alkaline treatment significantly decreased the apparent dielectric constant of NaCl-water solution in the pore, highlighting the rejection of sodium chloride. Contrariwise, the modification of the surface chemistry increased the apparent dielectric constant of NaF-water solution by promoting fluoride transmission. PMID:29160802

Modification of the Selectivity Properties of Tubular Ceramic Membranes after Alkaline Treatment.

PubMed

Dutournié, Patrick; Limousy, Lionel; Anquetil, Jérôme; Déon, Sébastien

2017-11-21

This work focuses on the selectivity modification of ceramic membranes after a mild alkaline treatment. Filtration of pure salt-water solutions was carried out with commercial titania membranes before and after the treatment. After treatment, the rejection of NaF significantly decreased, while the rejection of NaCl and NaBr increased. Additionally, NaI and Na₂SO₄ remained close to zero. Pore size and electrical charge being almost unchanged, only significant modifications in the dielectric effects can explain this modification of selectivity. Therefore, the surface chemistry and the interaction (nature and magnitude) with the solvent and with the species present in the solution appear to be modified by the alkaline treatment. This trend is also illustrated by discussing the electric and the dielectric properties that were numerically identified before and after treatment. The alkaline treatment significantly decreased the apparent dielectric constant of NaCl-water solution in the pore, highlighting the rejection of sodium chloride. Contrariwise, the modification of the surface chemistry increased the apparent dielectric constant of NaF-water solution by promoting fluoride transmission.

Scope & Limitations of Fmoc Chemistry SPPS-Based Approaches to the Total Synthesis of Insulin Lispro via Ester Insulin

PubMed Central

Dhayalan, Balamurugan; Mandal, Kalyaneswar; Rege, Nischay; Weiss, Michael A.; Eitel, Simon H.; Meier, Thomas; Schoenleber, Ralph O.; Kent, Stephen B.H.

2017-01-01

We have systematically explored three approaches based on Fmoc chemistry SPPS for the total chemical synthesis of the key depsipeptide intermediate for the efficient total chemical synthesis of insulin. The approaches used were: stepwise Fmoc chemistry SPPS; the ‘hybrid method’, in which maximally-protected peptide segments made by Fmoc chemistry SPPS are condensed in solution; and, native chemical ligation using peptide-thioester segments generated by Fmoc chemistry SPPS. A key building block in all three approaches was a Glu[Oβ(Thr)] ester-linked dipeptide equipped with a set of orthogonal protecting groups compatible with Fmoc chemistry SPPS. The most effective method for the preparation of the 51 residue ester-linked polypeptide chain of ester insulin was the use of unprotected peptide-thioester segments, prepared from peptide-hydrazides synthesized by Fmoc chemistry SPPS, and condensed by native chemical ligation. High resolution X-ray crystallography confirmed the disulfide pairings and three-dimensional structure of synthetic insulin lispro prepared from ester insulin lispro by this route. Further optimization of these pilot studies should yield an effective total chemical synthesis of insulin lispro (Humalog) based on peptide synthesis by Fmoc chemistry SPPS. PMID:27905149

Adsorption of a Textile Dye on Commercial Activated Carbon: A Simple Experiment to Explore the Role of Surface Chemistry and Ionic Strength

ERIC Educational Resources Information Center

Martins, Angela; Nunes, Nelson

2015-01-01

In this study, an adsorption experiment is proposed using commercial activated carbon as adsorbent and a textile azo dye, Mordant Blue-9, as adsorbate. The surface chemistry of the activated carbon is changed through a simple oxidation treatment and the ionic strength of the dye solution is also modified, simulating distinct conditions of water…

Flash Photolysis Experiment of o-Methyl Red as a Function of pH: A Low-Cost Experiment for the Undergraduate Physical Chemistry Lab

ERIC Educational Resources Information Center

Larsen, Molly C.; Perkins, Russell J.

2016-01-01

A low-cost, time-resolved spectroscopy experiment appropriate for third year physical chemistry students is presented. Students excite o-methyl red in basic solutions with a laser pointer and use a modular spectrometer with a CCD array detector to monitor the transient spectra as the higher-energy cis conformer of the molecule converts back to the…

ANALYTICAL CHEMISTRY DIVISION ANNUAL PROGRESS REPORT FOR PERIOD ENDING DECEMBER 31, 1961

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

1962-02-01

Research and development progress is reported on analytlcal instrumentation, dlssolver-solution analyses, special research problems, reactor projects analyses, x-ray and spectrochemical analyses, mass spectrometry, optical and electron microscopy, radiochemical analyses, nuclear analyses, inorganic preparations, organic preparations, ionic analyses, infrared spectral studies, anodization of sector coils for the Analog II Cyclotron, quality control, process analyses, and the Thermal Breeder Reactor Projects Analytical Chemistry Laboratory. (M.C.G.)

The 2017 Nobel Prize in Chemistry: cryo-EM comes of age.

PubMed

Shen, Peter S

2018-03-01

The 2017 Nobel Prize in Chemistry was awarded to Jacques Dubochet, Joachim Frank, and Richard Henderson for "developing cryo-electron microscopy (cryo-EM) for the high-resolution structure determination of biomolecules in solution." This feature article summarizes some of the major achievements leading to the development of cryo-EM and recent technological breakthroughs that have transformed the method into a mainstream tool for structure determination.

Yielding Unexpected Results: Precipitation of Ba[subscript3](PO[subscript4])[subscript2] and Implications for Teaching Solubility Principles in the General Chemistry Curriculum

ERIC Educational Resources Information Center

Hazen, Jeffery L.; Cleary, David A.

2014-01-01

Precipitation of barium phosphate from aqueous solutions of a barium salt and a phosphate salt forms the basis for a number of conclusions drawn in general chemistry. For example, the formation of a solid white precipitate is offered as evidence that barium phosphate is insoluble. Furthermore, analysis of the supernatant is used to illustrate the…

Linking soils and streams: Response of soil solution chemistry to simulated hurricane disturbance mirrors stream chemistry following a severe hurricane

Treesearch

William H. McDowell; Daniel Liptzin

2014-01-01

Understanding the drivers of forest ecosystem response to major disturbance events is an important topic in forest ecology and ecosystem management. Because of the multiple elements included in most major disturbances such as hurricanes, fires, or landslides, it is often difficult to ascribe a specific driver to the observed response. This is particularly true for the...

Application of a coupled ecosystem-chemical equilibrium model, DayCent-Chem, to stream and soil chemistry in a Rocky Mountain watershed

USGS Publications Warehouse

Hartman, M.D.; Baron, Jill S.; Ojima, D.S.

2007-01-01

Atmospheric deposition of sulfur and nitrogen species have the potential to acidify terrestrial and aquatic ecosystems, but nitrate and ammonium are also critical nutrients for plant and microbial productivity. Both the ecological response and the hydrochemical response to atmospheric deposition are of interest to regulatory and land management agencies. We developed a non-spatial biogeochemical model to simulate soil and surface water chemistry by linking the daily version of the CENTURY ecosystem model (DayCent) with a low temperature aqueous geochemical model, PHREEQC. The coupled model, DayCent-Chem, simulates the daily dynamics of plant production, soil organic matter, cation exchange, mineral weathering, elution, stream discharge, and solute concentrations in soil water and stream flow. By aerially weighting the contributions of separate bedrock/talus and tundra simulations, the model was able to replicate the measured seasonal and annual stream chemistry for most solutes for Andrews Creek in Loch Vale watershed, Rocky Mountain National Park. Simulated soil chemistry, net primary production, live biomass, and soil organic matter for forest and tundra matched well with measurements. This model is appropriate for accurately describing ecosystem and surface water chemical response to atmospheric deposition and climate change. ?? 2006 Elsevier B.V. All rights reserved.

Aggregation Kinetics of Diesel Soot Nanoparticles in Wet Environments.

PubMed

Chen, Chengyu; Huang, Weilin

2017-02-21

Soot produced during incomplete combustion consists mainly of carbonaceous nanoparticles (NPs) with severe adverse environmental and health effects, and its environmental fate and transport are largely controlled by aggregation. In this study, we examined the aggregation behavior for diesel soot NPs under aqueous condition in an effort to elucidate the fundamental processes that govern soot particle-particle interactions in wet environments such as rain droplets or surface aquatic systems. The influence of electrolytes and aqueous pH on colloidal stability of these NPs was investigated by measuring their aggregation kinetics in different aqueous solution chemistries. The results showed that the NPs had negatively charged surfaces and exhibited both reaction- and diffusion-limited aggregation regimes with rates depended upon solution chemistry. The aggregation kinetics data were in good agreement with the classic Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The critical coagulation concentrations (CCC) were quantified and the Hamaker constant was derived for the soot (1.4 × 10 -20 J) using the colloidal chemistry approach. The study indicated that, depending upon local aqueous chemistry, single soot NPs could remain stable against self-aggregation in typical freshwater environments and in neutral cloud droplets but are likely to aggregate under salty (e.g., estuaries) or acidic (e.g., acid rain droplets) aquatic conditions or both.

Constraints on ocean carbonate chemistry and pCO2 in the Archaean and Palaeoproterozoic

NASA Astrophysics Data System (ADS)

Blättler, C. L.; Kump, L. R.; Fischer, W. W.; Paris, G.; Kasbohm, J. J.; Higgins, J. A.

2017-01-01

One of the great problems in the history of Earth’s climate is how to reconcile evidence for liquid water and habitable climates on early Earth with the Faint Young Sun predicted from stellar evolution models. Possible solutions include a wide range of atmospheric and oceanic chemistries, with large uncertainties in boundary conditions for the evolution and diversification of life and the role of the global carbon cycle in maintaining habitable climates. Increased atmospheric CO2 is a common component of many solutions, but its connection to the carbon chemistry of the ocean remains unknown. Here we present calcium isotope data spanning the period from 2.7 to 1.9 billion years ago from evaporitic sedimentary carbonates that can test this relationship. These data, from the Tumbiana Formation, the Campbellrand Platform and the Pethei Group, exhibit limited variability. Such limited variability occurs in marine environments with a high ratio of calcium to carbonate alkalinity. We are therefore able to rule out soda ocean conditions during this period of Earth history. We further interpret this and existing data to provide empirical constraints for carbonate chemistry of the ancient oceans and for the role of CO2 in compensating for the Faint Young Sun.

Indirect photopatterning of functionalized organic monolayers via copper-catalyzed "click chemistry"

NASA Astrophysics Data System (ADS)

Williams, Mackenzie G.; Teplyakov, Andrew V.

2018-07-01

Solution-based lithographic surface modification of an organic monolayer on a solid substrate is attained based on selective area photo-reduction of copper (II) to copper (I) to catalyze the azide-alkyne dipolar cycloaddition "click" reaction. X-ray photoelectron spectroscopy is used to confirm patterning, and spectroscopic results are analyzed and supplemented with computational models to confirm the surface chemistry. It is determined that this surface modification approach requires irradiation of the solid substrate with all necessary components present in solution. This method requires only minutes of irradiation to result in spatial and temporal control of the covalent surface functionalization of a monolayer and offers the potential for wavelength tunability that may be desirable in many applications utilizing organic monolayers.

Fabrication, characterization and applications of iron selenide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hussain, Raja Azadar, E-mail: hussainazadar@yahoo.com; Badshah, Amin; Lal, Bhajan

This review article presents fabrication of FeSe by solid state reactions, solution chemistry routes, chemical vapor deposition, spray pyrolysis and chemical vapor transport. Different properties and applications such as crystal structure and phase transition, band structure, spectroscopy, superconductivity, photocatalytic activity, electrochemical sensing, and fuel cell activity of FeSe have been discussed. - Graphical abstract: Iron selenide can be synthesized by solid state reactions, chemical vapor deposition, solution chemistry routes, chemical vapor transport and spray pyrolysis. - Highlights: • Different fabrication methods of iron selenide (FeSe) have been reviewed. • Crystal structure, band structure and spectroscopy of FeSe have been discussed.more » • Superconducting, catalytic and fuel cell application of FeSe have been presented.« less

The route from problem to solution in multistep continuous flow synthesis of pharmaceutical compounds.

PubMed

Bana, Péter; Örkényi, Róbert; Lövei, Klára; Lakó, Ágnes; Túrós, György István; Éles, János; Faigl, Ferenc; Greiner, István

2017-12-01

Recent advances in the field of continuous flow chemistry allow the multistep preparation of complex molecules such as APIs (Active Pharmaceutical Ingredients) in a telescoped manner. Numerous examples of laboratory-scale applications are described, which are pointing towards novel manufacturing processes of pharmaceutical compounds, in accordance with recent regulatory, economical and quality guidances. The chemical and technical knowledge gained during these studies is considerable; nevertheless, connecting several individual chemical transformations and the attached analytics and purification holds hidden traps. In this review, we summarize innovative solutions for these challenges, in order to benefit chemists aiming to exploit flow chemistry systems for the synthesis of biologically active molecules. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ionic interactions in biological and physical systems: a variational treatment.

PubMed

Eisenberg, Bob

2013-01-01

Chemistry is about chemical reactions. Chemistry is about electrons changing their configurations as atoms and molecules react. Chemistry has for more than a century studied reactions as if they occurred in ideal conditions of infinitely dilute solutions. But most reactions occur in salt solutions that are not ideal. In those solutions everything (charged) interacts with everything else (charged) through the electric field, which is short and long range extending to the boundaries of the system. Mathematics has recently been developed to deal with interacting systems of this sort. The variational theory of complex fluids has spawned the theory of liquid crystals (or vice versa). In my view, ionic solutions should be viewed as complex fluids, particularly in the biological and engineering context. In both biology and electrochemistry ionic solutions are mixtures highly concentrated (to approximately 10 M) where they are most important, near electrodes, nucleic ids, proteins, active sites of enzymes, and ionic channels. Ca2+ is always involved in biological solutions because the concentration (really free energy per mole) of Ca2+ in a particular location is the signal that controls many biological functions. Such interacting systems are not simple fluids, and it is no wonder that analysis of interactions, such as the Hofmeister series, rooted in that tradition has not succeeded as one would hope. Here, we present a variational treatment of ard spheres in a frictional dielectric with the hope that such a treatment of an lectrolyte as a complex fluid will be productive. The theory automatically extends to spatially nonuniform boundary conditions and the nonequilibrium systems and flows they produce. The theory is unavoidably self-consistent since differential equations are derived (not assumed) from models of (Helmholtz free) nergy and dissipation of the electrolyte. The origin of the Hofmeister series is (in my view) an inverse problem that becomes well posed when enough data from disjoint experimental traditions are interpreted with a self-consistent theory.

Abiotic Organic Chemistry in Hydrothermal Systems.

NASA Astrophysics Data System (ADS)

Simoneit, B. R.; Rushdi, A. I.

2004-12-01

Abiotic organic chemistry in hydrothermal systems is of interest to biologists, geochemists and oceanographers. This chemistry consists of thermal alteration of organic matter and minor prebiotic synthesis of organic compounds. Thermal alteration has been extensively documented to yield petroleum and heavy bitumen products from contemporary organic detritus. Carbon dioxide, carbon monoxide, ammonia and sulfur species have been used as precursors in prebiotic synthesis experiments to organic compounds. These inorganic species are common components of hot spring gases and marine hydrothermal systems. It is of interest to further test their reactivities in reductive aqueous thermolysis. We have synthesized organic compounds (lipids) in aqueous solutions of oxalic acid, and with carbon disulfide or ammonium bicarbonate at temperatures from 175-400° C. The synthetic lipids from oxalic acid solutions consisted of n-alkanols, n-alkanoic acids, n-alkyl formates, n-alkanones, n-alkenes and n-alkanes, typically to C30 with no carbon number preferences. The products from CS2 in acidic aqueous solutions yielded cyclic thioalkanes, alkyl polysulfides, and thioesters with other numerous minor compounds. The synthesis products from oxalic acid and ammonium bicarbonate solutions were homologous series of n-alkyl amides, n-alkyl amines, n-alkanes and n-alkanoic acids, also to C30 with no carbon number predominance. Condensation (dehydration) reactions also occur under elevated temperatures in aqueous medium as tested by model reactions to form amide, ester and nitrile bonds. It is concluded that the abiotic formation of aliphatic lipids, condensation products (amides, esters, nitriles, and CS2 derivatives (alkyl polysulfides, cyclic polysulfides) is possible under hydrothermal conditions and warrants further studies.

Repeat synoptic sampling reveals drivers of change in carbon and nutrient chemistry of Arctic catchments

NASA Astrophysics Data System (ADS)

Zarnetske, J. P.; Abbott, B. W.; Bowden, W. B.; Iannucci, F.; Griffin, N.; Parker, S.; Pinay, G.; Aanderud, Z.

2017-12-01

Dissolved organic carbon (DOC), nutrients, and other solute concentrations are increasing in rivers across the Arctic. Two hypotheses have been proposed to explain these trends: 1. distributed, top-down permafrost degradation, and 2. discrete, point-source delivery of DOC and nutrients from permafrost collapse features (thermokarst). While long-term monitoring at a single station cannot discriminate between these mechanisms, synoptic sampling of multiple points in the stream network could reveal the spatial structure of solute sources. In this context, we sampled carbon and nutrient chemistry three times over two years in 119 subcatchments of three distinct Arctic catchments (North Slope, Alaska). Subcatchments ranged from 0.1 to 80 km2, and included three distinct types of Arctic landscapes - mountainous, tundra, and glacial-lake catchments. We quantified the stability of spatial patterns in synoptic water chemistry and analyzed high-frequency time series from the catchment outlets across the thaw season to identify source areas for DOC, nutrients, and major ions. We found that variance in solute concentrations between subcatchments collapsed at spatial scales between 1 to 20 km2, indicating a continuum of diffuse- and point-source dynamics, depending on solute and catchment characteristics (e.g. reactivity, topography, vegetation, surficial geology). Spatially-distributed mass balance revealed conservative transport of DOC and nitrogen, and indicates there may be strong in-stream retention of phosphorus, providing a network-scale confirmation of previous reach-scale studies in these Arctic catchments. Overall, we present new approaches to analyzing synoptic data for change detection and quantification of ecohydrological mechanisms in ecosystems in the Arctic and beyond.

Nucleation of metastable aragonite CaCO3 in seawater.

PubMed

Sun, Wenhao; Jayaraman, Saivenkataraman; Chen, Wei; Persson, Kristin A; Ceder, Gerbrand

2015-03-17

Predicting the conditions in which a compound adopts a metastable structure when it crystallizes out of solution is an unsolved and fundamental problem in materials synthesis, and one which, if understood and harnessed, could enable the rational design of synthesis pathways toward or away from metastable structures. Crystallization of metastable phases is particularly accessible via low-temperature solution-based routes, such as chimie douce and hydrothermal synthesis, but although the chemistry of the solution plays a crucial role in governing which polymorph forms, how it does so is poorly understood. Here, we demonstrate an ab initio technique to quantify thermodynamic parameters of surfaces and bulks in equilibrium with an aqueous environment, enabling the calculation of nucleation barriers of competing polymorphs as a function of solution chemistry, thereby predicting the solution conditions governing polymorph selection. We apply this approach to resolve the long-standing "calcite-aragonite problem"--the observation that calcium carbonate precipitates as the metastable aragonite polymorph in marine environments, rather than the stable phase calcite--which is of tremendous relevance to biomineralization, carbon sequestration, paleogeochemistry, and the vulnerability of marine life to ocean acidification. We identify a direct relationship between the calcite surface energy and solution Mg:Ca [corrected] ion concentrations, showing that the calcite nucleation barrier surpasses that of metastable aragonite in solutions with Mg:Ca ratios consistent with modern seawater, allowing aragonite to dominate the kinetics of nucleation. Our ability to quantify how solution parameters distinguish between polymorphs marks an important step toward the ab initio prediction of materials synthesis pathways in solution.

Nucleation of metastable aragonite CaCO 3 in seawater

DOE PAGES

Sun, Wenhao; Jayaraman, Saivenkataraman; Chen, Wei; ...

2015-03-04

Predicting the conditions in which a compound adopts a metastable structure when it crystallizes out of solution is an unsolved and fundamental problem in materials synthesis, and one which, if understood and harnessed, could enable the rational design of synthesis pathways toward or away from metastable structures. Crystallization of metastable phases is particularly accessible via low-temperature solution-based routes, such as chimie douce and hydrothermal synthesis, but although the chemistry of the solution plays a crucial role in governing which polymorph forms, how it does so is poorly understood. Here, we demonstrate an ab initio technique to quantify thermodynamic parameters ofmore » surfaces and bulks in equilibrium with an aqueous environment, enabling the calculation of nucleation barriers of competing polymorphs as a function of solution chemistry, thereby predicting the solution conditions governing polymorph selection. We apply this approach to resolve the long-standing “calcite–aragonite problem”––the observation that calcium carbonate precipitates as the metastable aragonite polymorph in marine environments, rather than the stable phase calcite––which is of tremendous relevance to biomineralization, carbon sequestration, paleogeochemistry, and the vulnerability of marine life to ocean acidification. We identify a direct relationship between the calcite surface energy and solution Mg–Ca ion concentrations, showing that the calcite nucleation barrier surpasses that of metastable aragonite in solutions with Mg:Ca ratios consistent with modern seawater, allowing aragonite to dominate the kinetics of nucleation. The ability to quantify how solution parameters distinguish between polymorphs marks an important step toward the ab initio prediction of materials synthesis pathways in solution.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Wenhao; Jayaraman, Saivenkataraman; Chen, Wei

Predicting the conditions in which a compound adopts a metastable structure when it crystallizes out of solution is an unsolved and fundamental problem in materials synthesis, and one which, if understood and harnessed, could enable the rational design of synthesis pathways toward or away from metastable structures. Crystallization of metastable phases is particularly accessible via low-temperature solution-based routes, such as chimie douce and hydrothermal synthesis, but although the chemistry of the solution plays a crucial role in governing which polymorph forms, how it does so is poorly understood. Here, we demonstrate an ab initio technique to quantify thermodynamic parameters ofmore » surfaces and bulks in equilibrium with an aqueous environment, enabling the calculation of nucleation barriers of competing polymorphs as a function of solution chemistry, thereby predicting the solution conditions governing polymorph selection. We apply this approach to resolve the long-standing “calcite–aragonite problem”––the observation that calcium carbonate precipitates as the metastable aragonite polymorph in marine environments, rather than the stable phase calcite––which is of tremendous relevance to biomineralization, carbon sequestration, paleogeochemistry, and the vulnerability of marine life to ocean acidification. We identify a direct relationship between the calcite surface energy and solution Mg–Ca ion concentrations, showing that the calcite nucleation barrier surpasses that of metastable aragonite in solutions with Mg:Ca ratios consistent with modern seawater, allowing aragonite to dominate the kinetics of nucleation. The ability to quantify how solution parameters distinguish between polymorphs marks an important step toward the ab initio prediction of materials synthesis pathways in solution.« less

Effectiveness of a Classroom Chemistry Demonstration Using the Cognitive Conflict Strategy

ERIC Educational Resources Information Center

Baddock, Maree; Bucat, Robert

2008-01-01

In an action research study, 66 students from Year 11 in an Australian school were shown the colour of methyl violet indicator in some hydrochloric acid solutions, and then in an acetic acid solution. The intent was to create a cognitive conflict, resolution of which would lead to an understanding of the concept "weak acid". Student…

Exploring Fundamental Concepts in Aqueous Solution Conductivity: A General Chemistry Laboratory Exercise

ERIC Educational Resources Information Center

Nyasulu, Frazier; Stevanov, Kelly; Barlag, Rebecca

2010-01-01

Using a conductivity sensor, a temperature sensor, and a datalogger, fundamental factors that affect conductivity are explored. These factors are (i) concentration, (ii) temperature, (iii) ion charge, and (iv) size and or mass of anion. In addition, the conductivities of a number of other solutions are measured. This lab has been designed to…

Algebra Word Problem Solving Approaches in a Chemistry Context: Equation Worked Examples versus Text Editing

ERIC Educational Resources Information Center

Ngu, Bing Hiong; Yeung, Alexander Seeshing

2013-01-01

Text editing directs students' attention to the problem structure as they classify whether the texts of word problems contain sufficient, missing or irrelevant information for working out a solution. Equation worked examples emphasize the formation of a coherent problem structure to generate a solution. Its focus is on the construction of three…

Measuring the Density of a Sugar Solution: A General Chemistry Experiment Using a Student-Prepared Unknown

ERIC Educational Resources Information Center

Peterson, Karen I.

2008-01-01

The experiment developed in this article addresses the concept of equipment calibration for reducing systematic error. It also suggests simple student-prepared sucrose solutions for which accurate densities are known, but not readily available to students. Densities are measured with simple glassware that has been calibrated using the density of…

Changes in soil solution chemistry of Andisols following invasion by bracken fern

Treesearch

J. L. Johnson-Maynard; P. A. McDaniel; D. E. Ferguson; A. L. Falen

1998-01-01

Disturbed areas within the Grand Fir Mosaic (GFM) ecosystem of northern Idaho show little to no natural conifer regeneration. Clear-cut sites are invaded quickly by bracken fern successional communities and seem to be in an arrested state of secondary succession. This study compared the soil solution composition of Andisols supporting bracken fern successional...

An Analytical Chemistry Experiment in Simultaneous Spectrophotometric Determination of Fe(III) and Cu(II) with Hexacyanoruthenate(II) Reagent.

ERIC Educational Resources Information Center

Mehra, M. C.; Rioux, J.

1982-01-01

Experimental procedures, typical observations, and results for the simultaneous analysis of Fe(III) and Cu(II) in a solution are discussed. The method is based on selective interaction between the two ions and potassium hexacyanoruthenate(II) in acid solution involving no preliminary sample preparations. (Author/JN)

Taking Advantage of a Corrosion Problem to Solve a Pollution Problem

ERIC Educational Resources Information Center

Palomar-Ramirez, Carlos F.; Bazan-Martinez, Jose A.; Palomar-Pardave, Manuel E.; Romero-Romo, Mario A.; Ramirez-Silva, Maria Teresa

2011-01-01

Some simple chemistry is used to demonstrate how Fe(II) ions, formed during iron corrosion in acid aqueous solution, can reduce toxic Cr(VI) species, forming soluble Cr(III) and Fe(III) ions. These ions, in turn, can be precipitated by neutralizing the solution. The procedure provides a treatment for industrial wastewaters commonly found in…

Simulated effects of reduced sulfur, nitrogen, and base cation deposition on soils and solutions in Southern Appalachian forests

Treesearch

D.W. Johnson; R.B. Susfalk; P.F. Brewer; W.T. Swank

1999-01-01

Effects of reduced deposition of N, S, and CB on nutrient pools, fluxes, soil, and soil solution chemistry were simulated for two Appalachian forest ecosystems using the nutrient cycling model. In the extremely acidic, N- and S-saturated red spruce (Picea rubens (Sarg.)) forest (Nolan Divide), reducing

Evaluation of the In Vitro Effect of Gold Nanorod Aspect Ratio, Surface Charge and Chemistry on Cellular Association and Cytotoxicity

DTIC Science & Technology

2016-03-28

Synthesis of GNRs ..............................................................................................................3 3.2 PEG...chemistry we can enhance their biocompatibility while maintaining their cellular uptake. 3 3.0 METHODS 3.1 Synthesis of GNRs MTAB GNRs (MTAB-1...chlorauric acid (0.1 M) was combined at room temperature with a growth solution of CTAB (0.1 M), chlorauric acid (0.1 M) silver nitrate (0.1 M) ascorbic

Large eddy simulation/dynamic thickened flame modeling of a high Karlovitz number turbulent premixed jet flame (Supplementary material).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, Wang; Wang, Haiou; Kuenne, Guido

This supplementary material complements the article and provides additional information to the chemical mechanism used in this work, boundary conditions for the LES con guration and table generation, comparisons of axial velocities, results from a LES/ nite-rate chemistry (FRC) approach, and results from the LES/DTF/SPF approach with a particular chemistry table that is generated using a single strained premixed amelet solution.

Reduction of Plutonium in Acidic Solutions by Mesoporous Carbons

DOE PAGES

Parsons-Moss, Tashi; Jones, Stephen; Wang, Jinxiu; ...

2015-12-19

Batch contact experiments with several porous carbon materials showed that carbon solids spontaneously reduce the oxidation state of plutonium in 1-1.5 M acid solutions, without significant adsorption. The final oxidation state and rate of Pu reduction varies with the solution matrix, and also depends on the surface chemistry and surface area of the carbon. It was demonstrated that acidic Pu(VI) solutions can be reduced to Pu(III) by passing through a column of porous carbon particles, offering an easy alternative to electrolysis with a potentiostat.

First-Principles Investigation of Lithium Polysulfide Structure and Behavior in Solution

DOE PAGES

Kamphaus, Ethan P.; Balbuena, Perla B.

2017-09-07

We present the Lithium-Sulfur battery is a promising next generation energy storage technology that could meet the demands of modern society with a theoretical specific energy near 2500 W h kg -1. However, this battery chemistry faces unique problems such as the parasitic polysulfide shuttle reaction which hinders battery performance severely. This shuttle phenomenon is caused by solubilities of intermediate reaction products in the electrolyte during the reduction chemistry of the battery. With molecular simulation and computational chemistry tools, we studied the thermodynamics, solvation structure, and dynamics of the long-chain lithium polysulfide species Li 2S 6 and Li 2S 8more » in dimethoxyethane and 1,3-dioxolane to gain a deeper fundamental understanding of this process. We determined the structure of the 1st solvation shell for Li + as well as those of Li 2S 6, Li 2S 8 closed and Li 2S 8 linear in pure solvents and solvents with extra Li + added. Finally, the lithium polysulfide species were found not to favor dissociation and would most likely exist as fully lithiated species in solution.« less

First-Principles Investigation of Lithium Polysulfide Structure and Behavior in Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kamphaus, Ethan P.; Balbuena, Perla B.

We present the Lithium-Sulfur battery is a promising next generation energy storage technology that could meet the demands of modern society with a theoretical specific energy near 2500 W h kg -1. However, this battery chemistry faces unique problems such as the parasitic polysulfide shuttle reaction which hinders battery performance severely. This shuttle phenomenon is caused by solubilities of intermediate reaction products in the electrolyte during the reduction chemistry of the battery. With molecular simulation and computational chemistry tools, we studied the thermodynamics, solvation structure, and dynamics of the long-chain lithium polysulfide species Li 2S 6 and Li 2S 8more » in dimethoxyethane and 1,3-dioxolane to gain a deeper fundamental understanding of this process. We determined the structure of the 1st solvation shell for Li + as well as those of Li 2S 6, Li 2S 8 closed and Li 2S 8 linear in pure solvents and solvents with extra Li + added. Finally, the lithium polysulfide species were found not to favor dissociation and would most likely exist as fully lithiated species in solution.« less

Protein Adsorption in Three Dimensions

PubMed Central

Vogler, Erwin A.

2011-01-01

Recent experimental and theoretical work clarifying the physical chemistry of blood-protein adsorption from aqueous-buffer solution to various kinds of surfaces is reviewed and interpreted within the context of biomaterial applications, especially toward development of cardiovascular biomaterials. The importance of this subject in biomaterials surface science is emphasized by reducing the “protein-adsorption problem” to three core questions that require quantitative answer. An overview of the protein-adsorption literature identifies some of the sources of inconsistency among many investigators participating in more than five decades of focused research. A tutorial on the fundamental biophysical chemistry of protein adsorption sets the stage for a detailed discussion of the kinetics and thermodynamics of protein adsorption, including adsorption competition between two proteins for the same adsorbent immersed in a binary-protein mixture. Both kinetics and steady-state adsorption can be rationalized using a single interpretive paradigm asserting that protein molecules partition from solution into a three-dimensional (3D) interphase separating bulk solution from the physical-adsorbent surface. Adsorbed protein collects in one-or-more adsorbed layers, depending on protein size, solution concentration, and adsorbent surface energy (water wettability). The adsorption process begins with the hydration of an adsorbent surface brought into contact with an aqueous-protein solution. Surface hydration reactions instantaneously form a thin, pseudo-2D interface between the adsorbent and protein solution. Protein molecules rapidly diffuse into this newly-formed interface, creating a truly 3D interphase that inflates with arriving proteins and fills to capacity within milliseconds at mg/mL bulk-solution concentrations CB. This inflated interphase subsequently undergoes time-dependent (minutes-to-hours) decrease in volume VI by expulsion of either-or-both interphase water and initially-adsorbed protein. Interphase protein concentration CI increases as VI decreases, resulting in slow reduction in interfacial energetics. Steady-state is governed by a net partition coefficient P=(/CBCI). In the process of occupying space within the interphase, adsorbing protein molecules must displace an equivalent volume of interphase water. Interphase water is itself associated with surface-bound water through a network of transient hydrogen bonds. Displacement of interphase water thus requires an amount of energy that depends on the adsorbent surface chemistry/energy. This “adsorption-dehydration” step is the significant free-energy cost of adsorption that controls the maximum amount of protein that can be adsorbed at steady state to a unit adsorbent-surface area (the adsorbent capacity). As adsorbent hydrophilicity increases, protein adsorption monotonically decreases because the energetic cost of surface dehydration increases, ultimately leading to no protein adsorption near an adsorbent water wettability (surface energy) characterized by a water contact angle θ → 65°. Consequently, protein does not adsorb (accumulate at interphase concentrations greater than bulk solution) to more hydrophilic adsorbents exhibiting θ < 65° . For adsorbents bearing strong Lewis acid/base chemistry such as ion-exchange resins, protein/surface interactions can be highly favorable, causing protein to adsorb in multilayers in a relatively thick interphase. A straightforward, three-component free energy relationship captures salient features of protein adsorption to all surfaces predicting that the overall free energy of protein adsorption ΔGadso is a relatively small multiple of thermal energy for any surface chemistry (except perhaps for bioengineered surfaces bearing specific ligands for adsorbing protein) because a surface chemistry that interacts chemically with proteins must also interact with water through hydrogen bonding. In this way, water moderates protein adsorption to any surface by competing with adsorbing protein molecules. This Leading Opinion ends by proposing several changes to the protein-adsorption paradigm that might advance answers to the three core questions that frame the “protein-adsorption problem” that is so fundamental to biomaterials surface science. PMID:22088888

An Empirical Approach to Predicting Effects of Climate Change on Stream Water Chemistry

NASA Astrophysics Data System (ADS)

Olson, J. R.; Hawkins, C. P.

2014-12-01

Climate change may affect stream solute concentrations by three mechanisms: dilution associated with increased precipitation, evaporative concentration associated with increased temperature, and changes in solute inputs associated with changes in climate-driven weathering. We developed empirical models predicting base-flow water chemistry from watershed geology, soils, and climate for 1975 individual stream sites across the conterminous USA. We then predicted future solute concentrations (2065 and 2099) by applying down-scaled global climate model predictions to these models. The electrical conductivity model (EC, model R2 = 0.78) predicted mean increases in EC of 19 μS/cm by 2065 and 40 μS/cm by 2099. However predicted responses for individual streams ranged from a 43% decrease to a 4x increase. Streams with the greatest predicted decreases occurred in the southern Rocky Mountains and Mid-West, whereas southern California and Sierra Nevada streams showed the greatest increases. Generally, streams in dry areas underlain by non-calcareous rocks were predicted to be the most vulnerable to increases in EC associated with climate change. Predicted changes in other water chemistry parameters (e.g., Acid Neutralization Capacity (ANC), SO4, and Ca) were similar to EC, although the magnitude of ANC and SO4 change was greater. Predicted changes in ANC and SO4 are in general agreement with those changes already observed in seven locations with long term records.

Differences in soil solution chemistry between soils amended with nanosized CuO or Cu reference materials: implications for nanotoxicity tests.

PubMed

McShane, Heather V A; Sunahara, Geoffrey I; Whalen, Joann K; Hendershot, William H

2014-07-15

Soil toxicity tests for metal oxide nanoparticles often include micrometer-sized oxide and metal salt treatments to distinguish between toxicity from nanometer-sized particles, non-nanometer-sized particles, and dissolved ions. Test result will be confounded if each chemical form has different effects on soil solution chemistry. We report on changes in soil solution chemistry over 56 days-the duration of some standard soil toxicity tests-in three soils amended with 500 mg/kg Cu as nanometer-sized CuO (nano), micrometer-sized CuO (micrometer), or Cu(NO3)2 (salt). In the CuO-amended soils, the log Cu2+ activity was initially low (minimum -9.48) and increased with time (maximum -5.20), whereas in the salt-amended soils it was initially high (maximum -4.80) and decreased with time (minimum -6.10). The Cu2+ activity in the nano-amended soils was higher than in the micrometer-amended soils for at least the first 11 days, and lower than in the salt-amended soils for at least 28 d. The pH, and dissolved Ca and Mg concentrations in the CuO-amended soils were similar, but the salt-amended soils had lower pH for at least 14 d, and higher Ca and Mg concentrations throughout the test. Soil pretreatments such as leaching and aging prior to toxicity tests are suggested.

Process for preparing energetic materials

DOEpatents

Simpson, Randall L [Livermore, CA; Lee, Ronald S [Livermore, CA; Tillotson, Thomas M [Tracy, CA; Hrubesh, Lawrence W [Pleasanton, CA; Swansiger, Rosalind W [Livermore, CA; Fox, Glenn A [Livermore, CA

2011-12-13

Sol-gel chemistry is used for the preparation of energetic materials (explosives, propellants and pyrotechnics) with improved homogeneity, and/or which can be cast to near-net shape, and/or made into precision molding powders. The sol-gel method is a synthetic chemical process where reactive monomers are mixed into a solution, polymerization occurs leading to a highly cross-linked three dimensional solid network resulting in a gel. The energetic materials can be incorporated during the formation of the solution or during the gel stage of the process. The composition, pore, and primary particle sizes, gel time, surface areas, and density may be tailored and controlled by the solution chemistry. The gel is then dried using supercritical extraction to produce a highly porous low density aerogel or by controlled slow evaporation to produce a xerogel. Applying stress during the extraction phase can result in high density materials. Thus, the sol-gel method can be used for precision detonator explosive manufacturing as well as producing precision explosives, propellants, and pyrotechnics, along with high power composite energetic materials.

Sol-Gel Manufactured Energetic Materials

DOEpatents

Simpson, Randall L.; Lee, Ronald S.; Tillotson, Thomas M.; Hrubesh, Lawrence W.; Swansiger, Rosalind W.; Fox, Glenn A.

2005-05-17

Sol-gel chemistry is used for the preparation of energetic materials (explosives, propellants and pyrotechnics) with improved homogeneity, and/or which can be cast to near-net shape, and/or made into precision molding powders. The sol-gel method is a synthetic chemical process where reactive monomers are mixed into a solution, polymerization occurs leading to a highly cross-linked three dimensional solid network resulting in a gel. The energetic materials can be incorporated during the formation of the solution or during the gel stage of the process. The composition, pore, and primary particle sizes, gel time, surface areas, and density may be tailored and controlled by the solution chemistry. The gel is then dried using supercritical extraction to produce a highly porous low density aerogel or by controlled slow evaporation to produce a xerogel. Applying stress during the extraction phase can result in high density materials. Thus, the sol-gel method can be used for precision detonator explosive manufacturing as well as producing precision explosives, propellants, and pyrotechnics, along with high power composite energetic materials.

Sol-gel manufactured energetic materials

DOEpatents

Simpson, Randall L.; Lee, Ronald S.; Tillotson, Thomas M.; Hrubesh, Lawrence W.; Swansiger, Rosalind W.; Fox, Glenn A.

2003-12-23

Sol-gel chemistry is used for the preparation of energetic materials (explosives, propellants and pyrotechnics) with improved homogeneity, and/or which can be cast to near-net shape, and/or made into precision molding powders. The sol-gel method is a synthetic chemical process where reactive monomers are mixed into a solution, polymerization occurs leading to a highly cross-linked three dimensional solid network resulting in a gel. The energetic materials can be incorporated during the formation of the solution or during the gel stage of the process. The composition, pore, and primary particle sizes, gel time, surface areas, and density may be tailored and controlled by the solution chemistry. The gel is then dried using supercritical extraction to produce a highly porous low density aerogel or by controlled slow evaporation to produce a xerogel. Applying stress during the extraction phase can result in high density materials. Thus, the sol-gel method can be used for precision detonator explosive manufacturing as well as producing precision explosives, propellants, and pyrotechnics, along with high power composite energetic materials.

Chemical conditions inside occluded regions on corroding aircraft aluminum alloys.

PubMed

Lewis, K S; Yuan, J; Kelly, R G

1999-07-30

Corrosion of aluminum alloy structures costs the US Air Force in the order of US$1 x 10(9) annually. Corrosion develops in areas of overlap such as aircraft lap-splice joints and under protective organic coatings. Capillary electrophoresis (CE) has been used to determine the local chemistries at these corrosion sites of solutions that were extracted using a microsampling system. Analysis of the local solution within lap-splice joints from aircraft has been performed in two ways: rehydration of corrosion products and direct microsampling. The solutions collected were analyzed with CE to quantitatively determine the species present during corrosion. The most common ions detected were Cl-, NO2-, NO3-, HCO3-, K+, Al3+, Ca2+, Na+ and Mg2+. Studies of the solution chemistry under local coating defects are required to understand coating failure and develop more durable coatings. A microsampling system and micro pH sensor were developed to extract solution from and measure pH in defects with diameters as small as 170 microns. Actively corroding defects contained high concentrations of Cl-, Al3+, Mg2+, Mn2+ and Cu2+ whereas only trace levels of Mg2+ were found in repassivated defects. The effects of these species on initiation and propagation of corrosion are discussed.

A context based approach using Green Chemistry/Bio-remediation principles to enhance interest and learning of organic chemistry in a high school AP chemistry classroom

NASA Astrophysics Data System (ADS)

Miller, Tricia

The ability of our planet to sustain life and heal itself is not as predictable as it used to be. Our need for educated future scientists who know what our planet needs, and can passionately apply that knowledge to find solutions should be at the heart of science education today. This study of learning organic chemistry through the lens of the environmental problem "What should be done with our food scraps?" explores student interest, and mastery of certain concepts in organic chemistry. This Green Chemistry/ Bio-remediation context-based teaching approach utilizes the Nature MillRTM, which is an indoor food waste composting machine, to learn about organic chemistry, and how this relates to landfill reduction possibilities, and resource production. During this unit students collected food waste from their cafeteria, and used the Nature MillRTM to convert food waste into compost. The use of these hands on activities, and group discussions in a context-based environment enhanced their interest in organic chemistry, and paper chromatography. According to a one-tailed paired T-test, the result show that this context-based approach is a significant way to increase both student interest and mastery of the content.

Scope and Limitations of Fmoc Chemistry SPPS-Based Approaches to the Total Synthesis of Insulin Lispro via Ester Insulin.

PubMed

Dhayalan, Balamurugan; Mandal, Kalyaneswar; Rege, Nischay; Weiss, Michael A; Eitel, Simon H; Meier, Thomas; Schoenleber, Ralph O; Kent, Stephen B H

2017-01-31

We have systematically explored three approaches based on 9-fluorenylmethoxycarbonyl (Fmoc) chemistry solid phase peptide synthesis (SPPS) for the total chemical synthesis of the key depsipeptide intermediate for the efficient total chemical synthesis of insulin. The approaches used were: stepwise Fmoc chemistry SPPS; the "hybrid method", in which maximally protected peptide segments made by Fmoc chemistry SPPS are condensed in solution; and, native chemical ligation using peptide-thioester segments generated by Fmoc chemistry SPPS. A key building block in all three approaches was a Glu[O-β-(Thr)] ester-linked dipeptide equipped with a set of orthogonal protecting groups compatible with Fmoc chemistry SPPS. The most effective method for the preparation of the 51 residue ester-linked polypeptide chain of ester insulin was the use of unprotected peptide-thioester segments, prepared from peptide-hydrazides synthesized by Fmoc chemistry SPPS, and condensed by native chemical ligation. High-resolution X-ray crystallography confirmed the disulfide pairings and three-dimensional structure of synthetic insulin lispro prepared from ester insulin lispro by this route. Further optimization of these pilot studies could yield an efficient total chemical synthesis of insulin lispro (Humalog) based on peptide synthesis by Fmoc chemistry SPPS. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Combined LAURA-UPS solution procedure for chemically-reacting flows. M.S. Thesis

NASA Technical Reports Server (NTRS)

Wood, William A.

1994-01-01

A new procedure seeks to combine the thin-layer Navier-Stokes solver LAURA with the parabolized Navier-Stokes solver UPS for the aerothermodynamic solution of chemically-reacting air flowfields. The interface protocol is presented and the method is applied to two slender, blunted shapes. Both axisymmetric and three dimensional solutions are included with surface pressure and heat transfer comparisons between the present method and previously published results. The case of Mach 25 flow over an axisymmetric six degree sphere-cone with a noncatalytic wall is considered to 100 nose radii. A stability bound on the marching step size was observed with this case and is attributed to chemistry effects resulting from the noncatalytic wall boundary condition. A second case with Mach 28 flow over a sphere-cone-cylinder-flare configuration is computed at both two and five degree angles of attack with a fully-catalytic wall. Surface pressures are seen to be within five percent with the present method compared to the baseline LAURA solution and heat transfers are within 10 percent. The effect of grid resolution is investigated and the nonequilibrium results are compared with a perfect gas solution, showing that while the surface pressure is relatively unchanged by the inclusion of reacting chemistry the nonequilibrium heating is 25 percent higher. The procedure demonstrates significant, order of magnitude reductions in solution time and required memory for the three dimensional case over an all thin-layer Navier-Stokes solution.

Algebraic Turbulence-Chemistry Interaction Model

NASA Technical Reports Server (NTRS)

Norris, Andrew T.

2012-01-01

The results of a series of Perfectly Stirred Reactor (PSR) and Partially Stirred Reactor (PaSR) simulations are compared to each other over a wide range of operating conditions. It is found that the PaSR results can be simulated by a PSR solution with just an adjusted chemical reaction rate. A simple expression has been developed that gives the required change in reaction rate for a PSR solution to simulate the PaSR results. This expression is the basis of a simple turbulence-chemistry interaction model. The interaction model that has been developed is intended for use with simple one-step global reaction mechanisms and for steady-state flow simulations. Due to the simplicity of the model there is very little additional computational cost in adding it to existing CFD codes.

Physical Organic Chemistry of Supramolecular Polymers

PubMed Central

Serpe, Michael J.; Craig, Stephen L.

2008-01-01

Unlike the case of traditional covalent polymers, the entanglements that determine properties of supramolecular polymers are defined by very specific, intermolecular interactions. Recent work using modular molecular platforms to probe the mechanisms underlying mechanical response of supramolecular polymers is reviewed. The contributions of supramolecular kinetics, thermodynamics, and conformational flexibility to supramolecular polymer properties in solutions of discrete polymers, in networks, and at interfaces, are described. Molecule-to-material relationships are established through methods reminiscent of classic physical organic chemistry. PMID:17279638

Engineering for Life Sciences: A Fruitful Collaboration Enabled by Chemistry.

PubMed

Niemeyer, Christof M

2017-02-13

"… The interaction of engineering and life sciences has a long history that is characterized by a mutual dependency. The role of chemistry in these developments is to connect the engineers' instrumentation with the life scientists' specimens. This very successful partnership will further continue to produce essential and innovative solutions for future challenges …" Read more in the Guest Editorial by Christof M. Niemeyer. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cyclic Polarization Behavior of ASTM A537-Cl.1 Steel in the Vapor Space Above Simulated Waste

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wiersma, B

2004-11-01

An assessment of the potential degradation mechanisms of Types I and II High-Level Waste (HLW) Tanks determined that pitting corrosion and stress corrosion cracking were the two most significant degradation mechanisms. Specifically, nitrate induced stress corrosion cracking was determined to be the principal degradation mechanism for the primary tank steel of non-stress relieved tanks. Controls on the solution chemistry have been in place to preclude the initiation and propagation of degradation in the tanks. However, recent experience has shown that steel not in contact with the bulk waste solution or slurry, but exposed to the ''vapor space'' above the bulkmore » waste, may be vulnerable to the initiation and propagation of degradation, including pitting and stress corrosion cracking. A program to resolve the issues associated with potential vapor space corrosion is in place. The objective of the program is to develop understanding of vapor space (VSC) and liquid/air interface (LAIC) corrosion to ensure a defensible technical basis to provide accurate corrosion evaluations with regard to vapor space and liquid/air interface corrosion (similar to current evaluations). There are several needs for a technically defensible basis with sufficient understanding to perform these evaluations. These include understanding of the (1) surface chemistry evolution, (2) corrosion response through coupon testing, and (3) mechanistic understanding through electrochemical studies. Experimentation performed in FY02 determined the potential for vapor space and liquid/air interface corrosion of ASTM A285-70 and ASTM A537-Cl.1 steels. The material surface characteristics, i.e. mill-scale, polished, were found to play a key role in the pitting response. The experimentation indicated that the potential for limited vapor space and liquid/air interface pitting exists at 1.5M nitrate solution when using chemistry controls designed to prevent stress corrosion cracking. Experimentation performed in FY03 quantified pitting rates as a function of material surface characteristics, including mill-scale and defects within the mill-scale. Testing was performed on ASTM A537-Cl.1 (normalized) steel, the material of construction of the Type III HLW tanks. The pitting rates were approximately 3 mpy for exposure above inhibited solutions, as calculated from the limited exposure times. This translates to a penetration time of 166 years for a 0.5-in tank wall provided that the pitting rate remains constant and the bulk solution chemistry is maintained within the L3 limit. The FY04 testing consisted of electrochemical testing to potentially lend insight into the surface chemistry and further understand the corrosion mechanism in the vapor space. Electrochemical testing lends insight into the corrosion processes through the determination of current potential relationships. The results of the electrochemical testing performed during FY04 are presented here.« less

Gibbs Energy Changes during Cobalt Complexation: A Thermodynamics Experiment for the General Chemistry Laboratory

ERIC Educational Resources Information Center

DeGrand, Michael J.; Abrams, M. Leigh; Jenkins, Judith L.; Welch, Lawrence E.

2011-01-01

By adding a large quantity of Cl[superscript -] to an aqueous solution of CoCl[subscript 2][multiplied by]6H[subscript 2]O, a mixture containing a red octahedral cobalt complex and a blue tetrahedral complex is produced. When the solution temperature is modified, the equilibrium constant, K[subscript eq], of the complexation reaction is shifted…

Persistent Self-Association of Solute Molecules in Solution.

PubMed

Tang, Weiwei; Mo, Huaping; Zhang, Mingtao; Parkin, Sean; Gong, Junbo; Wang, Jingkang; Li, Tonglei

2017-11-02

The structural evolvement of a solute determines the crystallization outcome. The self-association mechanism leading to nucleation, however, remains poorly understood. Our current study explored the solution chemistry of a model compound, tolfenamic acid (TFA), in three different solvents mainly by solution NMR. It was found that hydrogen-bonded pairs of solute-solute or solute-solvent stack with each through forming a much weaker π-π interaction as the concentration increases. Depending on the solvent, configurations of the solution species may be retained in the resultant crystal structure or undergo rearrangement. Yet, the π-π stacking is always retained in the crystal regardless of the solvent used for the crystallization. The finding suggests that nucleation not only involves the primary intermolecular interaction (hydrogen bonding) but also engages the secondary forces in the self-assembly process.

Time-dependent solution for axisymmetric flow over a blunt body with ideal gas, CF4, or equilibrium air chemistry

NASA Technical Reports Server (NTRS)

Hamilton, H. H., II; Spall, J. R.

1986-01-01

A time-asymptotic method has been used to obtain steady-flow solutions for axisymmetric inviscid flow over several blunt bodies including spheres, paraboloids, ellipsoids, and spherically blunted cones. Comparisons with experimental data and results of other computational methods have demonstrated that accurate solutions can be obtained using this approach. The method should prove useful as an analysis tool for comparing with experimental data and for making engineering calculations for blunt reentry vehicles.

Time-dependent solution for axisymmetric flow over a blunt body with ideal gas, CF4, or equilibrium air chemistry

NASA Astrophysics Data System (ADS)

Hamilton, H. H., II; Spall, J. R.

1986-07-01

A time-asymptotic method has been used to obtain steady-flow solutions for axisymmetric inviscid flow over several blunt bodies including spheres, paraboloids, ellipsoids, and spherically blunted cones. Comparisons with experimental data and results of other computational methods have demonstrated that accurate solutions can be obtained using this approach. The method should prove useful as an analysis tool for comparing with experimental data and for making engineering calculations for blunt reentry vehicles.

Long Term Stability in Thin Film Ferroelectric Memories

DTIC Science & Technology

1992-09-29

concentration is adjusted to IM. IM PT stock solution is prepared from Pb acetate and Ti isopropoxide dissolved in 2-MOE, and is added to the PMN stock...is necessary to understand that defect chemistry in detail. While PbTi0 3, PbZrO3 , and their solid- solutions , PZT, have not been thoroughly studied...methoxyethanol (2-MOE) is added. The ethanol and excess 2-MOE are removed by distillation. Pb precursor solution (Pb acetate in 2-MOE) is added and the 13

Using Chemistry and Color To Analyze Household Products: A 10-12 Hour Laboratory Project at the General Chemistry Level

NASA Astrophysics Data System (ADS)

Bosma, Wayne B.

1998-02-01

A general chemistry experiment is described in which the students use UV/Visible spectrometry as an analytical tool, for both compound identification and pH measurement. In the first portion of the experiment, the students compare spectra to determine which FD and C dyes are contained in household products. They furthermore use chromatography to separate the dyes in grape Kool-Aid, and analyze the products with the spectrometer. In the second portion of the experiment, the students use Beer's Law to determine the pH of solutions containing an acid/base indicator. The experiments are visually stimulating and provide a solid introduction to spectroscopy and perceived color.

A time-accurate algorithm for chemical non-equilibrium viscous flows at all speeds

NASA Technical Reports Server (NTRS)

Shuen, J.-S.; Chen, K.-H.; Choi, Y.

1992-01-01

A time-accurate, coupled solution procedure is described for the chemical nonequilibrium Navier-Stokes equations over a wide range of Mach numbers. This method employs the strong conservation form of the governing equations, but uses primitive variables as unknowns. Real gas properties and equilibrium chemistry are considered. Numerical tests include steady convergent-divergent nozzle flows with air dissociation/recombination chemistry, dump combustor flows with n-pentane-air chemistry, nonreacting flow in a model double annular combustor, and nonreacting unsteady driven cavity flows. Numerical results for both the steady and unsteady flows demonstrate the efficiency and robustness of the present algorithm for Mach numbers ranging from the incompressible limit to supersonic speeds.

Determination of acid ionization constants for weak acids by osmometry and the instrumental analysis self-evaluation feedback approach to student preparation of solutions

NASA Astrophysics Data System (ADS)

Kakolesha, Nyanguila

One focus of this work was to develop of an alternative method to conductivity for determining the acid ionization constants. Computer-controlled osmometry is one of the emerging analytical tools in industrial research and clinical laboratories. It is slowly finding its way into chemistry laboratories. The instrument's microprocessor control ensures shortened data collection time, repeatability, accuracy, and automatic calibration. The equilibrium constants of acetic acid, chloroacetic acid, bromoacetic acid, cyanoacetic acid, and iodoacetic acid have been measured using osmometry and their values compared with the existing literature values obtained, usually, from conductometric measurements. Ionization constant determined by osmometry for the moderately strong weak acids were in reasonably good agreement with literature values. The results showed that two factors, the ionic strength and the osmotic coefficient, exert opposite effects in solutions of such weak acids. Another focus of the work was analytical chemistry students solution preparation skills. The prevailing teacher-structured experiments leave little room for students' ingenuity in quantitative volumetric analysis. The purpose of this part of the study was to improve students' skills in making solutions using instrument feedback in a constructivist-learning model. After making some solutions by weighing and dissolving solutes or by serial dilution, students used the spectrophotometer and the osmometer to compare their solutions with standard solutions. Students perceived the instrument feedback as a nonthreatening approach to monitoring the development of their skill levels and liked to clarify their understanding through interacting with an instructor-observer. An assessment of the instrument feedback and the constructivist model indicated that students would assume responsibility for their own learning if given the opportunity. This study involved 167 students enrolled in Quantitative Chemical Analysis from fall 1998 through spring 2001. Surveys eliciting students' reactions to the instrument feedback approach showed an overwhelmingly positive response. The results of this research demonstrated that self-evaluation with instrumental feedback was a useful tool in helping students apply the knowledge they have acquired in lectures to the practice of chemistry. A demographic survey to determine whether part-time or full-time jobs had a negative impact on their experiment grades showed a small but significant correlation between hours worked and grade earned. However, the study showed that grades students earned on this experiment were predictive of overall semester lab grades.

An Effective Approach to Teaching Electrochemistry.

ERIC Educational Resources Information Center

Birss, Viola I.; Truax, D. Rodney

1990-01-01

An approach which may be useful for teaching electrochemistry in freshman college chemistry courses is presented. Discussed are the potential problems with teaching this subject and solutions provided by this approach. (CW)

Algorithms Bridging Quantum Computation and Chemistry

NASA Astrophysics Data System (ADS)

McClean, Jarrod Ryan

The design of new materials and chemicals derived entirely from computation has long been a goal of computational chemistry, and the governing equation whose solution would permit this dream is known. Unfortunately, the exact solution to this equation has been far too expensive and clever approximations fail in critical situations. Quantum computers offer a novel solution to this problem. In this work, we develop not only new algorithms to use quantum computers to study hard problems in chemistry, but also explore how such algorithms can help us to better understand and improve our traditional approaches. In particular, we first introduce a new method, the variational quantum eigensolver, which is designed to maximally utilize the quantum resources available in a device to solve chemical problems. We apply this method in a real quantum photonic device in the lab to study the dissociation of the helium hydride (HeH+) molecule. We also enhance this methodology with architecture specific optimizations on ion trap computers and show how linear-scaling techniques from traditional quantum chemistry can be used to improve the outlook of similar algorithms on quantum computers. We then show how studying quantum algorithms such as these can be used to understand and enhance the development of classical algorithms. In particular we use a tool from adiabatic quantum computation, Feynman's Clock, to develop a new discrete time variational principle and further establish a connection between real-time quantum dynamics and ground state eigenvalue problems. We use these tools to develop two novel parallel-in-time quantum algorithms that outperform competitive algorithms as well as offer new insights into the connection between the fermion sign problem of ground states and the dynamical sign problem of quantum dynamics. Finally we use insights gained in the study of quantum circuits to explore a general notion of sparsity in many-body quantum systems. In particular we use developments from the field of compressed sensing to find compact representations of ground states. As an application we study electronic systems and find solutions dramatically more compact than traditional configuration interaction expansions, offering hope to extend this methodology to challenging systems in chemical and material design.

Aggregation of asbestos fibers in water: role of solution chemistry

NASA Astrophysics Data System (ADS)

Wu, L.; Ortiz, C. P.; Jerolmack, D. J.

2016-12-01

Aggregation kinetics and stability of colloidal particles have been extensively studied using bulk techniques such as dynamic light scattering; these techniques involve large ensembles of particles and interpretation of results is difficult when particles are non-spherical and poorly characterized, as is always the case with non-ideal natural hazardous materials such as asbestos fibers. These difficulties hinder greatly progress on fundamental understanding of whether the classic colloidal aggregation theories can be applied to natural materials and how the heterogeneity of particles (e.g., shape) affects the colloidal aggregation kinetics and structure. By using in-situ microscopy and particle tracking techniques, we were able to observe the particle-by-particle growth of aggregated formed by elongated particles (synthetic glass rods and natural asbestos fibers) and demonstrated the rod-shaped geometry induced novel structures and growth dynamics that challenge existing theory. In this study, we continue to use asbestos as model system of elongated colloidal contaminant, and investigate the effects of changing solution chemistry (e.g., ionic strength, pH, and natural organic matter (NOM)), on growth dynamics and aggregates structure. The results show that aggregate growth curves are self-similar with a characteristic timescale that increases with increasing pH. By varying ionic strength for fixed pH values, we determine that the ccc is sensitive to pH. Fractal dimension decreases slightly with increasing pH and decreasing ionic strength, indicating that stronger inter-particle repulsion create sparser aggregates; however, the magnitude of the solution chemistry effects is much smaller than that of colloid shape. In monovalent solutions, regardless of their concentration, HA drastically reduces the aggregation kinetics of asbestos fiber. This work may lead to enhanced prediction of the colloidal contaminants' mobility in the environment, bioavailability, and toxicity to organisms.

Sol-gel chemistry-based Ucon-coated columns for capillary electrophoresis.

PubMed

Hayes, J D; Malik, A

1997-07-18

A sol-gel chemistry-based novel approach for the preparation of a Ucon-coated fused-silica capillary column in capillary electrophoresis is presented. In this approach the sol-gel process is carried out inside 25 microm I.D. fused-silica capillaries. The sol solution contained appropriate quantities of an alkoxide-based sol-gel precursor, a polymeric coating material (Ucon), a crosslinking reagent, a surface derivatizing reagent, controlled amounts of water and a catalyst dissolved in a suitable solvent system. The coating procedure involves filling a capillary with the sol solution and allowing the sol-gel process to proceed for an optimum period. Hydrolysis of the alkoxide precursor and polycondensation of the hydrolyzed products with the surface silanol groups and the hydroxy-terminated Ucon molecules lead to the formation of a surface-bonded sol-gel coating on the inner walls of the capillary. The thickness of the coated film can be controlled by varying the reaction time, coating solution composition and experimental conditions. Commercial availability of high purity sol-gel precursors (e.g., TEOS 99.999%), the ease of coating, run-to-run and column-to-column reproducibility, and long column lifetimes make sol-gel coating chemistry very much suitable for being applied in analytical microseparations column technology. Test samples of basic proteins and nucleotides were used to evaluate the column performance. These results show that the sol-gel coating scheme has allowed for the generation of bio-compatible surfaces characterized by high separation efficiencies in CE. For different types of solutes, the sol-gel coated Ucon column consistently provided migration time R.S.D. values of the order of 0.5%.

A decade of monitoring at Swiss Long-Term Forest Ecosystem Research (LWF) sites: can we observe trends in atmospheric acid deposition and in soil solution acidity?

PubMed

Pannatier, Elisabeth Graf; Thimonier, Anne; Schmitt, Maria; Walthert, Lorenz; Waldner, Peter

2011-03-01

Trends in atmospheric acid deposition and in soil solution acidity from 1995 or later until 2007 were investigated at several forest sites throughout Switzerland to assess the effects of air pollution abatements on deposition and the response of the soil solution chemistry. Deposition of the major elements was estimated from throughfall and bulk deposition measurements at nine sites of the Swiss Long-Term Forest Ecosystem Research network (LWF) since 1995 or later. Soil solution was measured at seven plots at four soil depths since 1998 or later. Trends in the molar ratio of base cations to aluminum (BC/Al) in soil solutions and in concentrations and fluxes of inorganic N (NO(3)-N + NH(4)-N), sulfate (SO(4)-S), and base cations (BC) were used to detect changes in soil solution chemistry. Acid deposition significantly decreased at three out of the nine study sites due to a decrease in total N deposition. Total SO(4)-S deposition decreased at the nine sites, but due to the relatively low amount of SO(4)-S load compared to N deposition, it did not contribute to decrease acid deposition significantly. No trend in total BC deposition was detected. In the soil solution, no trend in concentrations and fluxes of BC, SO(4)-S, and inorganic N were found at most soil depths at five out of the seven sites. This suggests that the soil solution reacted very little to the changes in atmospheric deposition. A stronger reduction in base cations compared to aluminum was detected at two sites, which might indicate that acidification of the soil solution was proceeding faster at these sites.

Chemistry of vaporization of refractory materials

NASA Technical Reports Server (NTRS)

Gilles, P. W.

1975-01-01

A discussion is given of the principles of physical chemistry important in vaporization studies, notably the concepts of equilibrium, phase behavior, thermodynamics, solid solution, and kinetics. The important factors influencing equilibrium vaporization phenomena are discussed and illustrated. A proper course of a vaporization study consisting of 9 stages is proposed. The important experimental techniques of Knudsen effusion, Langmuir vaporization and mass spectrometry are discussed. The principles, the factors, the course of a study and the experimental techniques and procedures are illustrated by recent work on the Ti-O system.

DNA-Mediated Electrochemistry

PubMed Central

Gorodetsky, Alon A.; Buzzeo, Marisa C.

2009-01-01

The base pair stack of DNA has been demonstrated as a medium for long range charge transport chemistry both in solution and at DNA-modified surfaces. This chemistry is exquisitely sensitive to structural perturbations in the base pair stack as occur with lesions, single base mismatches, and protein binding. We have exploited this sensitivity for the development of reliable electrochemical assays based on DNA charge transport at self-assembled DNA monolayers. Here we discuss the characteristic features, applications, and advantages of DNA-mediated electrochemistry. PMID:18980370

Installation Restoration Program. Phase II. Confirmation/Quantification Stage 1 for Nellis Air Force Base, Nevada.

DTIC Science & Technology

1985-08-09

chemicals from the sample, thereby preventing any effects on sample chemistry and cross-contamination of subsequent samples. The laboratory quality...14 Top 3011 4 16 1 Ca 1 ch4DChief ’aquifer (water-ticurinr 16 69 53 i Lrowm clay fo.mation) L 69 1 74 5 . atar oaandand ,ravei from..0.to .750. 74 1 127...significant fraction of the Chemistry Department’s work involves data processing. Mathematical models, based upon analysis of standard solutions or

Characteristic-based algorithms for flows in thermo-chemical nonequilibrium

NASA Technical Reports Server (NTRS)

Walters, Robert W.; Cinnella, Pasquale; Slack, David C.; Halt, David

1990-01-01

A generalized finite-rate chemistry algorithm with Steger-Warming, Van Leer, and Roe characteristic-based flux splittings is presented in three-dimensional generalized coordinates for the Navier-Stokes equations. Attention is placed on convergence to steady-state solutions with fully coupled chemistry. Time integration schemes including explicit m-stage Runge-Kutta, implicit approximate-factorization, relaxation and LU decomposition are investigated and compared in terms of residual reduction per unit of CPU time. Practical issues such as code vectorization and memory usage on modern supercomputers are discussed.

Viscosity of Common Seed and Vegetable Oils

NASA Astrophysics Data System (ADS)

Wes Fountain, C.; Jennings, Jeanne; McKie, Cheryl K.; Oakman, Patrice; Fetterolf, Monty L.

1997-02-01

Viscosity experiments using Ostwald-type gravity flow viscometers are not new to the physical chemistry laboratory. Several physical chemistry laboratory texts (1 - 3) contain at least one experiment studying polymer solutions or other well-defined systems. Several recently published articles (4 - 8) indicated the continued interest in using viscosity measurements in the teaching lab to illustrate molecular interpretation of bulk phenomena. Most of these discussions and teaching experiments are designed around an extensive theory of viscous flow and models of molecular shape that allow a full data interpretation to be attempted. This approach to viscosity experiments may not be appropriate for all teaching situations (e.g., high schools, general chemistry labs, and nonmajor physical chemistry labs). A viscosity experiment is presented here that is designed around common seed and vegetable oils. With the importance of viscosity to foodstuffs (9) and the importance of fatty acids to nutrition (10), an experiment using these common, recognizable oils has broad appeal.

The development of learning media of acid-base indicator from extract of natural colorant as an alternative media in learning chemistry

NASA Astrophysics Data System (ADS)

Nurhadi, Mukhamad; Wirhanuddin, Erwin, Muflihah, Erika, Farah; Widiyowati, Iis Intan

2017-03-01

The development of learning media of acid base indicator from extract of natural colorants as an alternative media in chemistry learning; acid-base solution by using creative problem solving model at SMA N 10 Samarinda has been done. This research aimed to create and develop the learning media from extract of natural colorants, measure its quality and effectiveness, and measure the quality of student learning outcome in acid-base solution topic by using that media. The development process used Analysis, Design, Development, Implementation, and Evaluation (ADDIE) method. The learning media of acid-base indicator was created in the form of box experiment. Its quality was in the range of very good and it was effectively applied in the learning and gave positive impact on the achievement of learning goals.

Validation of chemistry models employed in a particle simulation method

NASA Technical Reports Server (NTRS)

Haas, Brian L.; Mcdonald, Jeffrey D.

1991-01-01

The chemistry models employed in a statistical particle simulation method, as implemented in the Intel iPSC/860 multiprocessor computer, are validated and applied. Chemical relaxation of five-species air in these reservoirs involves 34 simultaneous dissociation, recombination, and atomic-exchange reactions. The reaction rates employed in the analytic solutions are obtained from Arrhenius experimental correlations as functions of temperature for adiabatic gas reservoirs in thermal equilibrium. Favorable agreement with the analytic solutions validates the simulation when applied to relaxation of O2 toward equilibrium in reservoirs dominated by dissociation and recombination, respectively, and when applied to relaxation of air in the temperature range 5000 to 30,000 K. A flow of O2 over a circular cylinder at high Mach number is simulated to demonstrate application of the method to multidimensional reactive flows.

Investigating surface chemistry-controlled dolomite precipitation in saline, alkaline, and dilute waters

NASA Astrophysics Data System (ADS)

Yoerg, A.; Roberts, J. A.

2017-12-01

Previous experiments have shown carboxylated organic matter facilitates dolomite precipitation at low temperature (< 80°C) in both modern and ancient seawater geochemistries. The efficacy of this mechanism in alternative chemical environments, particularly those typical of modern dolomitic environments, remains unclear. We investigated this question using a series of batch laboratory experiments ranging in duration from hours to several months. Experiments were conducted using fluids representative of environments where dolomite is found/thought to form in the modern, such as evaporative, alkaline lakes, sabkhas, and dilute mixing zones. Results indicate that while carboxylated organic matter promotes mineral precipitation in a variety of chemistries, the resultant mineralogy is primarily a function solution chemistry (i.e. saturation state). Specifically, our results suggest elevated alkalinity may be required to produce a high-Mg phase. In solutions where alkalinity is scarce, only amorphous carbonate phases form in association with organic matter, contrasting the Mg-bearing crystalline phases that result from highly alkaline solutions. Results of high-alkalinity, short-term experiments suggest that initially amorphous material is rapidly transformed into high and low-Mg phases in the presence of carboxylated organic matter, but that within days this mineralogy evolves. Longer timescales or elevated temperature may be necessary to produce an ordered dolomite phase. Additional results from longer term, steady-state experiments and additional analyses (Raman spectroscopy and tender energy spectroscopy) will shed further light on resultant mineralogy and this mechanism of dolomite precipitation.

Computer analysis of potentiometric data of complexes formation in the solution

NASA Astrophysics Data System (ADS)

Jastrzab, Renata; Kaczmarek, Małgorzata T.; Tylkowski, Bartosz; Odani, Akira

2018-02-01

The determination of equilibrium constants is an important process for many branches of chemistry. In this review we provide the readers with a discussion on computer methods which have been applied for elaboration of potentiometric experimental data generated during complexes formation in solution. The review describes both: general basis of modeling tools and examples of the use of calculated stability constants.

Phase Relations in Ternary Systems in the Subsolidus Region: Methods to Formulate Solid Solution Equations and to Find Particular Compositions

ERIC Educational Resources Information Center

Alvarez-Montan~o, Victor E.; Farías, Mario H.; Brown, Francisco; Mun~oz-Palma, Iliana C.; Cubillas, Fernando; Castillon-Barraza, Felipe F.

2017-01-01

A good understanding of ternary phase diagrams is required to advance and/or to reproduce experimental research in solid-state and materials chemistry. The aim of this paper is to describe the solutions to problems that appear when studying or determining ternary phase diagrams. A brief description of the principal features shown in phase diagrams…

Quality improvement on chemistry practicum courses through implementation of 5E learning cycle

NASA Astrophysics Data System (ADS)

Merdekawati, Krisna

2017-03-01

Two of bachelor of chemical education's competences are having practical skills and mastering chemistry material. Practicum courses are organized to support the competency achievement. Based on observation and evaluation, many problems were found in the implementation of practicum courses. Preliminary study indicated that 5E Learning Cycle can be used as an alternative solution in order to improve the quality of chemistry practicum course. The 5E Learning Cycle can provide positive influence on the achievement of the competence, laboratory skills, and students' understanding. The aim of the research was to describe the feasibility of implementation of 5E Learning Cycle on chemistry practicum courses. The research was based on phenomenology method in qualitative approach. The participants of the research were 5 person of chemistry laboratory manager (lecturers at chemistry and chemistry education department). They concluded that the 5E Learning Cycle could be implemented to improve the quality of the chemistry practicum courses. Practicum guides and assistant competences were organized to support the implementation of 5E Learning Cycle. It needed training for assistants to understand and implement in the stages of 5E Learning Cycle. Preparation of practical guidelines referred to the stages of 5E Learning Cycle, started with the introduction of contextual and applicable materials, then followed with work procedures that accommodate the stage of engagement, exploration, explanation, extension, and evaluation

Effects of atmospheric deposition nitrogen flux and its composition on soil solution chemistry from a red soil farmland, southeast China.

PubMed

Cui, Jian; Zhou, Jing; Peng, Ying; Chan, Andrew; Mao, Jingdong

2015-12-01

A detailed study on the solution chemistry of red soil in South China is presented. Data are collected from two simulated column-leaching experiments with an improved setup to evaluate the effects of atmospheric N deposition (ADN) composition and ADN flux on agricultural soil acidification using a (15)N tracer technique and an in situ soil solution sampler. The results show that solution pH values decline regardless of the increase of the NH4(+)/NO3(-) ratio in the ADN composition or ADN flux, while exchangeable Al(3+), Ca(2+), Mg(2+), and K(+) concentrations increase at different soil depths (20, 40, and 60 cm). Compared with the control, ADN (60 kg per ha per year N, NH4(+)/NO3(-) ratio of 2 : 1) decreases solution pH values, increases solution concentrations of NO3(-)-N, Al(3+), Ca(2+) and Mg(2+) at the middle and lower soil depths, and promotes their removal. NH4(+)-N was not detected in red soil solutions of all the three soil layers, which might be attributed to effects of nitrification, absorption and fixation in farmland red soil. Some of the NO3(-)-N concentrations at 40-60 cm soil depth exceed the safe drinking level of 10 mg L(-1), especially when the ADN flux is beyond 60 kg ha(-1) N. These features are critical for understanding the ADN agro-ecological effects, and for future assessment of ecological critical loads of ADN in red soil farmlands.

Coupling MD Simulations and X-ray Absorption Spectroscopy to Study Ions in Solution

NASA Astrophysics Data System (ADS)

Marcos, E. Sánchez; Beret, E. C.; Martínez, J. M.; Pappalardo, R. R.; Ayala, R.; Muñoz-Páez, A.

2007-12-01

The structure of ionic solutions is a key-point in understanding physicochemical properties of electrolyte solutions. Among the reduced number of experimental techniques which can supply direct information on the ion environment, X-ray Absorption techniques (XAS) have gained importance during the last decades although they are not free of difficulties associated to the data analysis leading to provide reliable structures. Computer simulations of ions in solution is a theoretical alternative to provide information on the solvation structure. Thus, the use of computational chemistry can increase the understanding of these systems although an accurate description of ionic solvation phenomena represents nowadays a significant challenge to theoretical chemistry. We present: (a) the assignment of features in the XANES spectrum to well defined structural motif in the ion environment, (b) MD-based evaluation of EXAFS parameters used in the fitting procedure to make easier the structural resolution, and (c) the use of the agreement between experimental and simulated XANES spectra to help in the choice of a given intermolecular potential for Computer Simulations. Chemical problems examined are: (a) the identification of the second hydration shell in dilute aqueous solutions of highly-charged cations, such as Cr3+, Rh3+, Ir3+, (b) the invisibility by XAS of certain structures characterized by Computer Simulations but exhibiting high dynamical behavior and (c) the solvation of Br- in acetonitrile.

Coupling MD Simulations and X-ray Absorption Spectroscopy to Study Ions in Solution

NASA Astrophysics Data System (ADS)

Marcos, E. Sánchez; Beret, E. C.; Martínez, J. M.; Pappalardo, R. R.; Ayala, R.; Muñoz-Páez, A.

2007-11-01

The structure of ionic solutions is a key-point in understanding physicochemical properties of electrolyte solutions. Among the reduced number of experimental techniques which can supply direct information on the ion environment, X-ray Absorption techniques (XAS) have gained importance during the last decades although they are not free of difficulties associated to the data analysis leading to provide reliable structures. Computer simulations of ions in solution is a theoretical alternative to provide information on the solvation structure. Thus, the use of computational chemistry can increase the understanding of these systems although an accurate description of ionic solvation phenomena represents nowadays a significant challenge to theoretical chemistry. We present: (a) the assignment of features in the XANES spectrum to well defined structural motif in the ion environment, (b) MD-based evaluation of EXAFS parameters used in the fitting procedure to make easier the structural resolution, and (c) the use of the agreement between experimental and simulated XANES spectra to help in the choice of a given intermolecular potential for Computer Simulations. Chemical problems examined are: (a) the identification of the second hydration shell in dilute aqueous solutions of highly-charged cations, such as Cr3+, Rh3+, Ir3+, (b) the invisibility by XAS of certain structures characterized by Computer Simulations but exhibiting high dynamical behavior and (c) the solvation of Br- in acetonitrile.

Adsorption of Dyes in Studying the Surface Chemistry of Ultradispersed Diamond

NASA Astrophysics Data System (ADS)

Khokhlova, T. D.; Yunusova, G. R.; Lanin, S. N.

2018-05-01

The effect the surface chemistry of ultradispersed diamond (UDD) has on the adsorption of watersoluble dyes is considered. A comparison is made to adsorption on graphitized thermal carbon black (GTCB), which has a homogeneous and nonporous surface. The adsorption isotherms of dyes and the dependence of the adsorption on the pH of solutions are measured. It is found that UDD adsorbs acid (anionic) dyes—acid orange (AO) and acid anthraquinone blue (AAB)—but barely adsorbs a basic (cationic) dye, methylene blue (MB), because of the predominance of positively charged basic groups on the surface of UDD. The maximum adsorption of AO is much lower on UDD than on GTCB, while the maximum adsorption of AAB is similar for both surfaces. The adsorption of AO on UDD depends strongly on the pH of the solution, while the adsorption of AAB is independent of this parameter. It is suggested that the adsorption of AAB is determined not only by ionic and hydrophobic interactions but also by coordination interactions with impurity metal ions on a UDD surface. It is concluded that the adsorption of dyes characterizes the chemistry of a UDD surface with high sensitivity.

Microfluidic Platform for High-throughput Screening of Leach Chemistry.

PubMed

Yang, Die; Priest, Craig

2018-06-20

We demonstrate an optofluidic screening platform for studying thiosulfate leaching of Au in a transparent microchannel. The approach permits in situ (optical) monitoring of Au thickness, reduced reagent use, rapid optimization of reagent chem-istry, screening of temperature, and determination of the activation energy. The results demonstrate the critical importance of the (1) preparation and storage of the leach solution, (2) deposition and annealing of the Au film, and (3) lixiviant chem-istry. The density of sputter deposited Au films decreased with depth resulting in accelerating leach rates during experiments. Atomic leach rates were determined and were constant throughout each experiment. Annealing above 270 °C was found to prevent leaching, which can be attributed to diffusion of the chromium adhesion layer into the Au film. The optofluidic analysis revealed leach rates that are sensitive to the stoichiometric ratio of thiosulphate, ammonia and copper in the leach solution, and optimized for 10 mM CuSO 4 , 1 M Na 2 S 2 O 3 and 1 M NH 4 OH. The temperature dependence of the leach rate gave an apparent activation energy of ~ 40 kJ.mol -1 , based on Arrhenius' relationship.

Quantum Chemistry in Great Britain: Developing a Mathematical Framework for Quantum Chemistry

NASA Astrophysics Data System (ADS)

Simões, Ana; Gavroglu, Kostas

By 1935 quantum chemistry was already delineated as a distinct sub-discipline due to the contributions of Fritz London, Walter Heitler, Friedrich Hund, Erich Hückel, Robert Mulliken, Linus Pauling, John van Vleck and John Slater. These people are credited with showing that the application of quantum mechanics to the solution of chemical problems was, indeed, possible, especially so after the introduction of a number of new concepts and the adoption of certain approximation methods. And though a number of chemists had started talking of the formation of theoretical or, even, mathematical chemistry, a fully developed mathematical framework of quantum chemistry was still wanting. The work of three persons in particular-of John E. Lennard-Jones, Douglas R. Hartree, and Charles Alfred Coulson-has been absolutely crucial in the development of such a framework. In this paper we shall discuss the work of these three researchers who started their careers in the Cambridge tradition of mathematical physics and who at some point of their careers all became professors of applied mathematics. We shall argue that their work consisted of decisive contributions to the development of such a mathematical framework for quantum chemistry.

Soil-solution chemistry in a low-elevation spruce-fir ecosystem, Howland, Maine

USGS Publications Warehouse

Fernandez, Ivan J.; Lawrence, Gregory B.; Son, Yowhan

1995-01-01

Soil solutions were collected monthly by tension and zero-tension lysimeters in a low-elevation red spruce stand in east-central Maine from May 1987 through December 1992. Soil solutions collected by Oa tension lysimeters had higher concentrations of most constituents than the Oa zero-tension lysimeters. In Oa horizon soil solutions growing season concentrations for SO4, Ca, and Mg averaged 57, 43, and 30 μmol L−1 in tension lysimeters, and 43, 28, and 19 μmol L−1 in zero-tension lysimeters, respectively. Because tension lysimeters remove water held by the soil at tensions up to 10 kPa, solutions are assumed to have more time to react with the soil compared to freely draining solutions collected by zero-tension lysimeters. Solutions collected in the Bs horizon by both types of collectors were similar which was attributed to the frequency of time periods when the water table was above the Bs lysimeters. Concentrations of SO4 and NO3 at this site were lower than concentrations reported for most other eastern U.S. spruce-fir sites, but base cation concentrations fell in the same range. Aluminum concentrations in this study were also lower than reported for other sites in the eastern U.S. and Ca/Al ratios did not suggest inhibition of Ca uptake by roots. Concentrations of SO4, Ca, K, and Cl decreased significantly in both the Oa and Bs horizons over the 56-month sampling period, which could reflect decreasing deposition rates for sulfur and base cations, climatic influences, or natural variation. A longer record of measured fluxes will be needed to adequately define temporal trends in solution chemistry and their causes.

Peroxidase-mediated polymerization of 1-naphthol: impact of solution pH and ionic strength.

PubMed

Bhandari, Alok; Xu, Fangxiang; Koch, David E; Hunter, Robert P

2009-01-01

Peroxidase-mediated oxidation has been proposed as a treatment method for naphthol-contaminated water. However, the impact of solution chemistry on naphthol polymerization and removal has not been documented. This research investigated the impact of pH and ionic strength on peroxidase-mediated removal of 1-naphthol in completely mixed batch reactors. The impact of hydrogen peroxide to 1-naphthol ratio and activity of horseradish peroxidase was also studied. Size exclusion chromatography was used to estimate the molecular weight distribution of oligomeric products, and liquid chromatography/mass spectrometry was used to estimate product structure. Naphthol transformation decreased with ionic strength, and substrate removal was lowest at neutral pHs. Solution pH influenced the size and the composition of the oligomeric products. An equimolar ratio of H(2)O(2):naphthol was sufficient for optimal naphthol removal. Polymerization products included naphthoquinones and oligomers derived from two, three, and four naphthol molecules. Our results illustrate the importance of water chemistry when considering a peroxidase-based approach for treatment of naphthol-contaminated waters.

Differential natural organic matter fouling of ceramic versus polymeric ultrafiltration membranes.

PubMed

Lee, Seung-Jin; Kim, Jae-Hong

2014-01-01

Ceramic ultrafiltration membranes has drawn increasing attention in drinking water treatment sectors as an alternative to traditional polymeric counterparts, yet only limited information has been made available about the characteristics of ceramic membrane fouling by natural organic matter. The effects of solution chemistry including ionic strength, divalent ion concentration and pH on the flux behavior were comparatively evaluated for ceramic and polymeric ultrafiltration of synthetic water containing model natural organic matter. Filtration characteristics were further probed via resistance-in-series model analysis, fouling visualization using quantum dots, batch adsorption test, contact angle measurement, solute-membrane surface adhesion force measurement, and quantitative comparison of fouling characteristics between ceramic and polymeric membranes. The results collectively suggested that the effects of solution chemistry on fouling behavior of ceramic membranes were generally similar to polymeric counterparts in terms of trends, while the extent varied significantly depending on water quality parameters. Lower fouling tendency and enhanced cleaning efficiency were observed with the ceramic membrane, further promoting the potential for ceramic membrane application to surface water treatment. Copyright © 2013 Elsevier Ltd. All rights reserved.

Large-scale separation of single-walled carbon nanotubes by electronic type using click chemistry

NASA Astrophysics Data System (ADS)

Um, Jo-Eun; Song, Sun Gu; Yoo, Pil J.; Song, Changsik; Kim, Woo-Jae

2018-01-01

Single-walled carbon nanotubes (SWCNTs) can be either metallic or semiconducting, making their separation critical for applications in nanoelectronics, biomedical materials, and solar cells. Herein, we investigate a novel solution-phase separation method based on click chemistry (azide-alkyne Huisgen cycloaddition) and determine its efficiency and scalability. In this method, metallic SWCNTs in metallic/semiconducting SWCNT mixtures are selectively functionalized with alkyne groups by being reacted with 4-propargyloxybenezenediazonium tetrafluoroborate. Subsequently, silica nanoparticles are functionalized with azide groups and reacted with alkyne-bearing metallic SWCNTs in the SWCNT mixture in the presence of a Cu catalyst. As a result, metallic SWCNTs are anchored on silica powder, whereas non-functionalized semiconducting SWCNTs remain in solution. Low-speed centrifugation effectively removes the silica powder with attached metallic SWCNTs, furnishing a solution of highly pure semiconducting SWCNTs, as confirmed by Raman and UV-vis/near-infrared absorption measurements. This novel separation scheme exhibits the advantage of simultaneously separating both metallic and semiconducting SWCNTs from their mixtures, being cost-effective and therefore applicable at an industrial scale.

Colorful Chemistry.

ERIC Educational Resources Information Center

Williams, Suzanne

1991-01-01

Described is an color-making activity where students use food coloring, eyedroppers, and water to make various colored solutions. Included are the needed materials and procedures. Students are asked to write up the formulas for making their favorite color. (KR)

Laboratory Applications of the Vortex Tube.

ERIC Educational Resources Information Center

Bruno, Thomas J.

1987-01-01

Discussed are a brief explanation of the function of the vortex tube and some applications for the chemistry laboratory. It is a useful and inexpensive solution to many small-scale laboratory heating and cooling applications. (RH)

Illustrating Chemical Concepts through Food Systems: Introductory Chemistry Experiments.

ERIC Educational Resources Information Center

Chambers, E., IV; Setser, C. S.

1980-01-01

Demonstrations involving foods that illustrate chemical concepts are described, including vaporization of liquids and Graham's law of diffusion, chemical reaction rates, adsorption, properties of solutions, colloidal dispersions, suspensions, and hydrogen ion concentration. (CS)

Determination of Quantum Chemistry Based Force Fields for Molecular Dynamics Simulations of Aromatic Polymers

NASA Technical Reports Server (NTRS)

Jaffe, Richard; Langhoff, Stephen R. (Technical Monitor)

1995-01-01

Ab initio quantum chemistry calculations for model molecules can be used to parameterize force fields for molecular dynamics simulations of polymers. Emphasis in our research group is on using quantum chemistry-based force fields for molecular dynamics simulations of organic polymers in the melt and glassy states, but the methodology is applicable to simulations of small molecules, multicomponent systems and solutions. Special attention is paid to deriving reliable descriptions of the non-bonded and electrostatic interactions. Several procedures have been developed for deriving and calibrating these parameters. Our force fields for aromatic polyimide simulations will be described. In this application, the intermolecular interactions are the critical factor in determining many properties of the polymer (including its color).

The radiation chemistry of ionic liquids: A review

DOE PAGES

Mincher, Bruce J.; Wishart, James F.

2014-07-03

Ionic liquids have received increasing attention as media for radiochemical separations. Recent literature includes examinations of the efficiencies and mechanisms of the solvent extraction of lanthanides, actinides and fission products into ionic liquid solutions. For radiochemical applications, including as replacement solvents for nuclear fuel reprocessing, a thorough understanding of the radiation chemistry of ionic liquids will be required. Such an understanding can be achieved based on a combination of steady-state radiolysis experiments coupled with post-irradiation product identification and pulse-radiolysis experiments to acquire kinetic information. These techniques allow for the elucidation of radiolytic mechanisms. This contribution reviews the current ionic liquidmore » radiation chemistry literature as it affects separations, with these considerations in mind.« less

Students' integration of multiple representations in a titration experiment

NASA Astrophysics Data System (ADS)

Kunze, Nicole M.

A complete understanding of a chemical concept is dependent upon a student's ability to understand the microscopic or particulate nature of the phenomenon and integrate the microscopic, symbolic, and macroscopic representations of the phenomenon. Acid-base chemistry is a general chemistry topic requiring students to understand the topics of chemical reactions, solutions, and equilibrium presented earlier in the course. In this study, twenty-five student volunteers from a second semester general chemistry course completed two interviews. The first interview was completed prior to any classroom instruction on acids and bases. The second interview took place after classroom instruction, a prelab activity consisting of a titration calculation worksheet, a titration computer simulation, or a microscopic level animation of a titration, and two microcomputer-based laboratory (MBL) titration experiments. During the interviews, participants were asked to define and describe acid-base concepts and in the second interview they also drew the microscopic representations of four stages in an acid-base titration. An analysis of the data showed that participants had integrated the three representations of an acid-base titration to varying degrees. While some participants showed complete understanding of acids, bases, titrations, and solution chemistry, other participants showed several alternative conceptions concerning strong acid and base dissociation, the formation of titration products, and the dissociation of soluble salts. Before instruction, participants' definitions of acid, base, and pH were brief and consisted of descriptive terms. After instruction, the definitions were more scientific and reflected the definitions presented during classroom instruction.

Groundwater solute chemistry and arsenic fate in aquifer of Brahmaputra river basin, India: Controls of geology and tectonic setting

NASA Astrophysics Data System (ADS)

Verma, S.; Mukherjee, A.; Mahanta, C.

2015-12-01

Elevated arsenic (As) concentrations in groundwater of the river Brahmaputra basin of India has been largely undocumented, and unexplored. Hydrogeochemical investigations in three different tectono-geomorphic settings of the basin i.e. the northwestern and northern part (located along foothills of the Eastern Himalayas) and southern part (in vicinity of Naga-thrust belt) demonstrate regional variability of groundwater chemistry and redox conditions with geology. Shallow alluvial aquifers of southern part, which are mainly composed of black/dark grey clay and fine sands are affected by high arsenic concentration whereas groundwater from sandy aquifer in the northwestern and northern part have comparatively lower As concentrations. Stable isotopes (δ2H and δ18O) in groundwater indicate suggest that some evaporation may have taken place through recharging water in the study areas. The major-ion composition shows that groundwater of northwestern and northern part are dominated by Ca2+-HCO3-, Ca2+-Na+-HCO3 while southern part is dominated by Na+-Ca2+-HCO3- hydrochemical facies. Molar ratios suggested that most groundwater solutes of northwestern and northern parts were derived from both silicate weathering and carbonate dissolution and have not been affected by cation exchange, while silicate weathering process dominates in aquifers of southern where cation exchange probably has little influence on water chemistry. Thermodynamic calculations show that most of samples fall along the equilibrium line between kaolinite and smectite. While, positive correlations of As with Fe, Mn and HCO3 were observed in northwestern and northern parts aquifers, no consistent correlation of As with any parameter was observed in the aquifers of southern part. Therefore, the results of the study clearly indicate geological control (i.e. change in lithofacies, tectonic set-up) on groundwater chemistry and distribution of redox-sensitive solutes such as As.

Selected specific rates of reactions of transients from water in aqueous solution. III. Hydroxyl radical and perhydroxyl radical and their radical ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ross, F; Ross, A B

1977-01-01

Rates of reactions of OH and HO/sub 2/ with organic and inorganic molecules, ions and transients in aqueous solution have been tabulated, as well as the rates for the corresponding radical ions in aqueous solution (O/sup -/ and O/sub 2//sup -/). Most of the rates have been obtained by radiation chemistry methods, both pulsed and steady-state; data from photochemistry and thermal methods are also included. Rates for over one thousand reactions are listed.

Antimicrobial and other properties of a new stabilized alkaline glutaraldehyde disinfectant/sterilizer.

PubMed

Miner, N A; McDowell, J W; Willcockson, G W; Bruckner, N I; Stark, R L; Whitmore, E J

1977-04-01

The properties of stabilized alkaline 2% glutaraldehyde solution (SGS) are discussed. SGS is discussed with regard to its chemistry, antimicrobial properties, organic soil resistance, toxicity, corrosivity and chemical stability. SGS retains the maximum antimicrobial activity of alkaline glutaraldehyde solutions and the chemical stability heretofore observed only with acidic glutaraldehyde solutions. These improvements, along with the inherent resistance of glutaraldehyde to neutralization by organic soil, allow SGS to be continuously used for 14 days in situations of high dilution, or 28 days in situations of low dilution.

Seeing Chemistry through Sound: A Submersible Audible Light Sensor for Observing Chemical Reactions for Students Who Are Blind or Visually Impaired

ERIC Educational Resources Information Center

Supalo, Cary A.; Kreuter, Rodney A.; Musser, Aaron; Han, Josh; Briody, Erika; McArtor, Chip; Gregory, Kyle; Mallouk, Thomas E.

2006-01-01

In order to enable students who are blind and visually impaired to observe chemical changes in solutions, a hand-held device was designed to output light intensity as an audible tone. The submersible audible light sensor (SALS) creates an audio signal by which one can observe reactions in a solution in real time, using standard laboratory…

21 CFR 314.440 - Addresses for applications and abbreviated applications.

Code of Federal Regulations, 2011 CFR

2011-04-01

... mail code for the Office of Generic Drugs is HFD-600, the mail codes for the Divisions of Chemistry I... leukapheresis; (3) Blood component processing solutions and shelf life extenders; and (4) Oxygen carriers. [50...

21 CFR 314.440 - Addresses for applications and abbreviated applications.

Code of Federal Regulations, 2013 CFR

2013-04-01

... mail code for the Office of Generic Drugs is HFD-600, the mail codes for the Divisions of Chemistry I... leukapheresis; (3) Blood component processing solutions and shelf life extenders; and (4) Oxygen carriers. [50...

21 CFR 314.440 - Addresses for applications and abbreviated applications.

Code of Federal Regulations, 2014 CFR

2014-04-01

... mail code for the Office of Generic Drugs is HFD-600, the mail codes for the Divisions of Chemistry I... leukapheresis; (3) Blood component processing solutions and shelf life extenders; and (4) Oxygen carriers. [50...

21 CFR 314.440 - Addresses for applications and abbreviated applications.

Code of Federal Regulations, 2012 CFR

2012-04-01

... mail code for the Office of Generic Drugs is HFD-600, the mail codes for the Divisions of Chemistry I... leukapheresis; (3) Blood component processing solutions and shelf life extenders; and (4) Oxygen carriers. [50...

The Blue Bottle Experiment--Simple Demonstration of Self-Organization.

ERIC Educational Resources Information Center

Adamcikova, L'ubica; Sevcik, Peter

1998-01-01

Explains a way of observing pattern formation in the Blue Bottle chemistry demonstration by pouring a solution containing sodium hydroxide, glucose, and dye into a Petri dish and placing the dish on an overhead projector. (WRM)

Simple Perturbation Example for Quantum Chemistry.

ERIC Educational Resources Information Center

Goodfriend, P. L.

1985-01-01

Presents a simple example that illustrates various aspects of the Rayleigh-Schrodinger perturbation theory. The example is a particularly good one because it is straightforward and can be compared with both the exact solution and with experimental data. (JN)

Molecular Modeling of Environmentally Important Processes: Reduction Potentials

ERIC Educational Resources Information Center

Lewis, Anne; Bumpus, John A.; Truhlar, Donald G.; Cramer, Christopher J.

2004-01-01

The increasing use of computational quantum chemistry in the modeling of environmentally important processes is described. The employment of computational quantum mechanics for the prediction of oxidation-reduction potential for solutes in an aqueous medium is discussed.

UNIQUE CHEMISTRY SOLUTIONS TO REGIONAL ISSUES

EPA Science Inventory

Many of ORD's research projects relate to broad scientific themes, such as biological and chemical indicators or computational toxicology .Others are discrete studies resulting from requests from or informal contacts with clients and collaborators. This poster presents a montage ...

Synthesis and Characterization of Three Dimensional Nanostructures Based on Interconnected Carbon Nanomaterials

NASA Astrophysics Data System (ADS)

Koizumi, Ryota

This thesis addresses various types of synthetic methods for novel three dimensional nanomaterials and nanostructures based on interconnected carbon nanomaterials using solution chemistry and chemical vapor deposition (CVD) methods. Carbon nanotube (CNT) spheres with porous and scaffold structures consisting of interconnected CNTs were synthesized by solution chemistry followed by freeze-drying, which have high elasticity under nano-indentation tests. This allows the CNT spheres to be potentially applied to mechanical dampers. CNTs were also grown on two dimensional materials--such as reduced graphene oxide (rGO) and hexagonal boron nitride (h-BN)--by CVD methods, which are chemically interconnected. CNTs on rGO and h-BN interconnected structures performed well as electrodes for supercapacitors. Furthermore, unique interconnected flake structures of alpha-phase molybdenum carbide were developed by a CVD method. The molybdenum carbide can be used for a catalyst of hydrogen evolution reaction activity as well as an electrode for supercapacitors.

Adsorption of benzene and toluene from aqueous solutions onto activated carbon and its acid and heat treated forms: influence of surface chemistry on adsorption.

PubMed

Wibowo, N; Setyadhi, L; Wibowo, D; Setiawan, J; Ismadji, S

2007-07-19

The influence of surface chemistry and solution pH on the adsorption of benzene and toluene on activated carbon and its acid and heat treated forms were studied. A commercial coal-based activated carbon F-400 was chosen as carbon parent. The carbon samples were obtained by modification of F-400 by means of chemical treatment with HNO3 and thermal treatment under nitrogen flow. The treatment with nitric acid caused the introduction of a significant number of oxygenated acidic surface groups onto the carbon surface, while the heat treatment increases the basicity of carbon. The pore characteristics were not significantly changed after these modifications. The dispersive interactions are the most important factor in this adsorption process. Activated carbon with low oxygenated acidic surface groups (F-400Tox) has the best adsorption capacity.

Riparian control of stream-water chemistry: Implications for hydrochemical basin models

USGS Publications Warehouse

Hooper, R.P.; Aulenbach, Brent T.; Burns, Douglas A.; McDonnell, J.; Freer, J.; Kendall, C.; Beven, K.

1998-01-01

End-member mixing analysis has been used to determine the hydrological structure for basin hydrochemical models at several catchments. Implicit in this use is the assumption that controlling end members have been identified, and that these end members represent distinct landscape locations. At the Panola Mountain Research Watershed, the choice of controlling end members was supported when a large change in the calcium and sulphate concentration of one of the end members was reflected in the stream water. More extensive sampling of groundwater and soil water indicated, however, that the geographic extent of the contributing end members was limited to the riparian zone. Hillslope solutions were chemically distinct from the riparian solutions and did not appear to make a large contribution to streamflow. The dominant control of the riparian zone on stream-water chemistry suggests that hydrological flow paths cannot be inferred from stream-water chemical dynamics.

Chemistry and adhesive properties of poly(arylene ether)s containing heterocyclic units

NASA Technical Reports Server (NTRS)

Connell, John W.

1991-01-01

Novel poly(arylene ether)s containing heterocyclic units were prepared, characterized, and evaluated as adhesives and composite matrices. The polymers were prepared by reacting a heterocyclic bisphenol with an activated aromatic dihalide in a polar aprotic solvent, using potassium carbonate. The polymerizations were generally carried out in N,N-dimethylacetamide at 155 C. In some cases, where the polymers were semicrystalline, higher temperatures and thus higher boiling solvents were necessary to keep the polymers in solution. Heterocyclic rings incorporated into the poly(arylene ether) backbone include phenylquinoxaline, phenylimidazole, benzimidazole, benzoxazole, 1,3,4-oxadiazole, and 1,2,4-triazole. The polymers were characterized by differential scanning calorimetry, solution viscosity, X-ray diffraction, thin film, and adhesive and (in some cases) composite properties. The glass transition temperatures, crystalline melt temperature, solubility, and mechanical properties varied depending upon the heterocyclic ring. The chemistry and properties of these materials are discussed.

Microscale Chemistry in a Plastic Petri Dish: Preparation and Chemical Properties of Chlorine Gas

NASA Astrophysics Data System (ADS)

Choi, Martin M. F.

2002-08-01

This experiment demonstrates some of the chemistry of chlorine on a microscale, about the size of a water droplet. Chlorine gas was prepared from an acidified bleach solution in a plastic petri dish. The chlorine gas generated in situ reacted with other chemical reagents in the dish by diffusion. Some of the oxidizing properties and bleaching power of chlorine gas were shown visually and could be observed within 10 minutes. These experiments provide suitable hands-on experience for students at secondary-school level.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nelson, A. J.; Voss, L. F.; Beck, P. R.

We subjected device-grade TlBr to various chemical treatments used in room temperature radiation detector fabrication to determine the resulting surface composition and electronic structure. As-polished TlBr was treated separately with HCl, SOCl 2, Br:MeOH and HF solutions. High-resolution photoemission measurements on the valence band electronic structure and Tl 4f, Br 3d, Cl 2p and S 2p core lines were used to evaluate surface chemistry and shallow heterojunction formation. Surface chemistry and valence band electronic structure were correlated with the goal of optimizing the long-term stability and radiation response.

Data on snow chemistry of the Cascade-Sierra Nevada Mountains

USGS Publications Warehouse

Laird, L.B.; Taylor, Howard E.; Lombard, R.E.

1986-01-01

Snow chemistry data were measured for solutes found in snow core samples collected from the Cascade-Sierra Nevada Mountains from late February to mid-March 1983. The data are part of a study to assess geographic variations in atmospheric deposition in Washington, Oregon, and California. The constituents and properties include pH and concentrations of hydrogen ion, calcium, magnesium, sodium, potassium, chloride, sulfate, nitrate, fluoride, phosphate, ammonium, iron, aluminum, manganese, copper, cadmium, lead, and dissolved organic carbon. Concentrations of arsenic and bromide were below the detection limit. (USGS)

Physicochemical controls on absorbed water film thickness in unsaturated geological media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tokunaga, T.

2011-06-14

Adsorbed water films commonly coat mineral surfaces in unsaturated soils and rocks, reducing flow and transport rates. Therefore, it is important to understand how adsorbed film thickness depends on matric potential, surface chemistry, and solution chemistry. Here, the problem of adsorbed water film thickness is examined through combining capillary scaling with the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Novel aspects of this analysis include determining capillary influences on film thicknesses, and incorporating solution chemistry-dependent electrostatic potential at air-water interfaces. Capillary analysis of monodisperse packings of spherical grains provided estimated ranges of matric potentials where adsorbed films are stable, and showed that pendular ringsmore » within drained porous media retain most of the 'residual' water except under very low matric potentials. Within drained pores, capillary contributions to thinning of adsorbed films on spherical grains are shown to be small, such that DLVO calculations for flat surfaces are suitable approximations. Hamaker constants of common soil minerals were obtained to determine ranges of the dispersion component to matric potential-dependent film thickness. The pressure component associated with electrical double layer forces was estimated using the compression and linear superposition approximations. The pH-dependent electrical double layer pressure component is the dominant contribution to film thicknesses at intermediate values of matric potential, especially in lower ionic strength solutions (< 10 mol m{sup -3}) on surfaces with higher magnitude electrostatic potentials (more negative than - 50 mV). Adsorbed water films are predicted to usually range in thickness from 1 to 20 nm in drained pores and fractures of unsaturated environments.« less

Physicochemical controls on adsorbed water film thickness in unsaturated geological media

NASA Astrophysics Data System (ADS)

Tokunaga, Tetsu K.

2011-08-01

Adsorbed water films commonly coat mineral surfaces in unsaturated soils and rocks, reducing flow and transport rates. Therefore, it is important to understand how adsorbed film thickness depends on matric potential, surface chemistry, and solution chemistry. Here the problem of adsorbed water film thickness is examined by combining capillary scaling with the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Novel aspects of this analysis include determining capillary influences on film thicknesses and incorporating solution chemistry-dependent electrostatic potential at air-water interfaces. Capillary analysis of monodisperse packings of spherical grains provided estimated ranges of matric potentials where adsorbed films are stable and showed that pendular rings within drained porous media retain most of the "residual" water except under very low matric potentials. Within drained pores, capillary contributions to thinning of adsorbed films on spherical grains are shown to be small, such that DLVO calculations for flat surfaces are suitable approximations. Hamaker constants of common soil minerals were obtained to determine ranges of the dispersion component to matric potential-dependent film thickness. The pressure component associated with electrical double-layer forces was estimated using the compression and linear superposition approximations. The pH-dependent electrical double-layer pressure component is the dominant contribution to film thicknesses at intermediate values of matric potential, especially in lower ionic strength solutions (<10 mol m-3) on surfaces with higher-magnitude electrostatic potentials (more negative than ≈-50 mV). Adsorbed water films are predicted to usually range in thickness from ≈1 to 20 nm in drained pores and fractures of unsaturated environments.

Thermodynamics and Solubilities of Salts of Dipositive Ions.

ERIC Educational Resources Information Center

Riley, Gary F.; Eberhardt, William H.

1979-01-01

In this general chemistry experiment students calculate changes in free energy of formation of inorganic salts from the free energy of formation of ions. Then they test the conclusions of their calculations by mixing solutions of the ions. (BB)

40 CFR 796.1050 - Absorption in aqueous solution: Ultraviolet/visible spectra.

Code of Federal Regulations, 2010 CFR

2010-07-01

... organic solvent should be used (methanol preferred). (3) The acid medium should have a pH of less than 2...) Milazzo, G., Caroli, S., Palumbo-Doretti, M., Violante, N., Analytical Chemistry, 49: 711 (1977). (2...

Using Simple Quadratic Equations to Estimate Equilibrium Concentrations of an Acid

ERIC Educational Resources Information Center

Brilleslyper, Michael A.

2004-01-01

Application of quadratic equations to standard problem in chemistry like finding equilibrium concentrations of ions in an acid solution is explained. This clearly shows that pure mathematical analysis has meaningful applications in other areas as well.

Band gap and composition engineering on a nanocrystal (BCEN) in solution.

PubMed

Peng, Xiaogang

2010-11-16

Colloidal nanocrystals with "artificial" composition and electron band structure promise to expand the fields of nanomaterials and inorganic chemistry. Despite their promise as functional materials, the fundamental science associated with the synthesis, characterization, and properties of colloidal nanocrystals is still in its infancy and deserves systematic study. Furthermore, such studies are important for our basic understanding of crystallization, surface science, and solid state chemistry. "Band gap and composition engineering on a nanocrystal" (BCEN) refers to the synthesis of a colloidal nanocrystal with composition and/or electron energy band structure that are not found in natural bulk crystals. The BCEN nanostructure shown in the Figure includes a magnetic domain for the separation and recycling of the complex nanostructure, a photoactivated catalytic center, and an additional chemical catalytic center. A thin but porous film (such as a silicate) might be coated onto the nanocrystal, both to provide chemical stability and to isolate the reaction processes from the bulk solution. This example is a catalytic complex analogous to an enzyme that facilitates two sequential reactions in a microenvironment different from bulk solution. The synthesis of colloidal nanocrystals has advanced by a quantum leap in the past two decades. The field now seems ready to extend colloidal nanocrystal synthesis into the BCEN regime. Although BCEN is a very new branch of synthetic chemistry, this Account describes advances in related synthetic and characterization techniques that can serve as a useful starting point for this new area of investigation. To put these ideas into context, this Account compares this new field with organic synthesis, the most developed branch in synthetic chemistry. The structural and functional diversity of organic compounds results from extending design and synthesis beyond the construction of natural organic compounds. If this idea also holds true for inorganic nanocrystals, "artificial" BCEN nanocrystals will most likely outperform the inorganic nanocrystals with naturally occurring structure and composition. If the importance of artificial molecules is a positive lesson from organic synthesis, the practical disadvantage of organic chemistry is that purification can prove much more time consuming than the reaction itself. To get around this problem, colloidal nanocrystal chemists can attempt to avoid these potential purification challenges in the early stages of synthetic method development.

Elaboration of Copper-Oxygen Mediated C–H Activation Chemistry in Consideration of Future Fuel and Feedstock Generation

PubMed Central

Lee, Jung Yoon; Karlin, Kenneth D

2015-01-01

To contribute solutions for current energy concerns, improvements in the efficiency of C-H bond cleavage chemistry, e.g., selective oxidation of methane to methanol, could minimize losses in natural gas usage or produce feedstocks for fuels. Oxidative C-H activation is also a component of polysaccharide degradation, affording alternative biofuels from abundant biomass. Thus, an understanding of active-site chemistry in copper monooxygenases, those activating strong C-H bonds is briefly reviewed. Then, recent advances in the synthesis-generation and study of various copper-oxygen intermediates are highlighted. Of special interest are cupric-superoxide, Cu-hydroperoxo and Cu-oxy complexes. Such investigations can contribute to an enhanced future application of C-H oxidation or oxygenation processes using air, as concerning societal energy goals. PMID:25756327

Ice Melting to Release Reactants in Solution Syntheses.

PubMed

Wei, Hehe; Huang, Kai; Zhang, Le; Ge, Binghui; Wang, Dong; Lang, Jialiang; Ma, Jingyuan; Wang, Da; Zhang, Shuai; Li, Qunyang; Zhang, Ruoyu; Hussain, Naveed; Lei, Ming; Liu, Li-Min; Wu, Hui

2018-03-19

Aqueous solution syntheses are mostly based on mixing two solutions with different reactants. It is shown that freezing one solution and melting it in another solution provides a new interesting strategy to mix chemicals and to significantly change the reaction kinetics and thermodynamics. For example, a precursor solution containing a certain concentration of AgNO 3 was frozen and dropped into a reductive NaBH 4 solution at about 0 °C. The ultra-slow release of reactants was successfully achieved. An ice-melting process can be used to synthesize atomically dispersed metals, including cobalt, nickel, copper, rhodium, ruthenium, palladium, silver, osmium, iridium, platinum, and gold, which can be easily extended to other solution syntheses (such as precipitation, hydrolysis, and displacement reactions) and provide a generalized method to redesign the interphase reaction kinetics and ion diffusion in wet chemistry. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gender differences in response to questions on the australian national chemistry quiz

NASA Astrophysics Data System (ADS)

Walding, Richard; Fogliani, Charles; Over, Ray; Bain, John D.

In contrast to the attention given to the relative levels of achievement of boys and girls in mathematics, the question of whether there are sex differences in the solution of chemistry questions has not attracted much attention. This study compares the performance of boys and girls in the Australian National Chemistry Quiz (Chem Quiz), a multiple-choice test conducted by the Royal Australian Chemical Institute. The analyses were based on results from 27,000 students in Years 11 and 12 and 16,000 students in Year 10 who completed the Chem Quiz in 1991. Although some questions in the Chem Quiz were solved equally well by boys and girls, on many questions boys outperformed girls. The extreme case was a question answered correctly by 67% of Year 10 boys in contrast to 48% of Year 10 girls. Several reasons why boys and girls might differ in the rates they solve at least some chemistry questions are discussed, and directions for identifying the nature, extent, and basis for sex differences are outlined.

Competition between organics and bromide at the aqueous solution-air interface as seen from ozone uptake kinetics and X-ray photoelectron spectroscopy.

PubMed

Lee, Ming-Tao; Brown, Matthew A; Kato, Shunsuke; Kleibert, Armin; Türler, Andreas; Ammann, Markus

2015-05-14

A more detailed understanding of the heterogeneous chemistry of halogenated species in the marine boundary layer is required. Here, we studied the reaction of ozone (O3) with NaBr solutions in the presence and absence of citric acid (C6H8O7) under ambient conditions. Citric acid is used as a proxy for oxidized organic material present at the ocean surface or in sea spray aerosol. On neat NaBr solutions, the observed kinetics is consistent with bulk reaction-limited uptake, and a second-order rate constant for the reaction of O3 + Br(-) is 57 ± 10 M(-1) s(-1). On mixed NaBr-citric acid aqueous solutions, the uptake kinetics was faster than that predicted by bulk reaction-limited uptake and also faster than expected based on an acid-catalyzed mechanism. X-ray photoelectron spectroscopy (XPS) on a liquid microjet of the same solutions at 1.0 × 10(-3)-1.0 × 10(-4) mbar was used to obtain quantitative insight into the interfacial composition relative to that of the bulk solutions. It revealed that the bromide anion becomes depleted by 30 ± 10% while the sodium cation gets enhanced by 40 ± 20% at the aqueous solution-air interface of a 0.12 M NaBr solution mixed with 2.5 M citric acid in the bulk, attributed to the role of citric acid as a weak surfactant. Therefore, the enhanced reactivity of bromide solutions observed in the presence of citric acid is not necessarily attributable to a surface reaction but could also result from an increased solubility of ozone at higher citric acid concentrations. Whether the acid-catalyzed chemistry may have a larger effect on the surface than in the bulk to offset the effect of bromide depletion also remains open.

Degradation of dichlorvos using hydrodynamic cavitation based treatment strategies.

PubMed

Joshi, Ravi K; Gogate, Parag R

2012-05-01

The degradation of an aqueous solution of dichlorvos, a commonly used pesticide in India, has been systematically investigated using hydrodynamic cavitation reactor. All the experiments have been carried out using a 20 ppm solution of commercially available dichlorvos. The effect of important operating parameters such as inlet pressure (over a range 3-6 bar), temperature (31 °C, 36 °C and 39 °C) and pH (natural pH = 5.7 and acidic pH = 3) on the extent of degradation has been investigated initially. It has been observed that an optimum value of pressure gives maximum degradation whereas low temperature and pH of 3 are favorable. Intensification studies have been carried out using different additives such as hydrogen peroxide, carbon tetrachloride, and Fenton's reagent. Use of hydrogen peroxide and carbon tetrachloride resulted in the enhancement of the extent of degradation at optimized conditions but significant enhancement was obtained with the combined use of hydrodynamic cavitation and Fenton's chemistry. The maximum extent of degradation as obtained by using a combination of hydrodynamic cavitation and Fenton's chemistry was 91.5% in 1h of treatment time. The present work has conclusively established that hydrodynamic cavitation in combination with Fenton's chemistry can be effectively used for the degradation of dichlorvos. Copyright © 2011 Elsevier B.V. All rights reserved.

The role of chemistry in the energy challenge.

PubMed

Schlögl, Robert

2010-02-22

Chemistry with its key targets of providing materials and processes for conversion of matter is at the center stage of the energy challenge. Most energy conversion systems work on (bio)chemical energy carriers and require for their use suitable process and material solutions. The enormous scale of their application demands optimization beyond the incremental improvement of empirical discoveries. Knowledge-based systematic approaches are mandatory to arrive at scalable and sustainable solutions. Chemistry for energy, "ENERCHEM" contributes in many ways already today to the use of fossil energy carriers. Optimization of these processes exemplified by catalysis for fuels and chemicals production or by solid-state lightning can contribute in the near future substantially to the dual challenge of energy use and climate protection being in fact two sides of the same challenge. The paper focuses on the even greater role that ENERCHEM will have to play in the era of renewable energy systems where the storage of solar energy in chemical carries and batteries is a key requirement. A multidisciplinary and diversified approach is suggested to arrive at a stable and sustainable system of energy conversion processes. The timescales for transformation of the present energy scenario will be decades and the resources will be of global economic dimensions. ENERCHEM will have to provide the reliable basis for such technologies based on deep functional understanding.

Uniqueness of a solution of a steady state photochemical problem: Applications to Mars

NASA Technical Reports Server (NTRS)

Krasnopolsky, Vladimir A.

1995-01-01

Based on the conservation of chemical elements in chemical reactions, a rule is proved that the number of boundary conditions given by densities and/or nonzero velocities should not be less than the number of chemical elements in the system, and the boundary conditions for species given by densities and velocities should include all elements in the system. Applications of this rule to Mars are considered. It is shown that the problem of the CO2-H2O chemistry in the lower and middle atmosphere of Mars, say, in the range of 0-80 km does not have a unique solution, if only CO2 and H2O densities are given at the lower boundary, and the remaining boundary conditions are fluxes. Two examples of models of this type are discussed. Two models of the photochemistry of the Martian atmosphere, with and without nitrogen chemistry, are considered. The oxygen nonthermal escape ratio of 1.2 x 10(exp 8)/cu cm/s is given at 240 km and is balanced with the total hydrogen escape rate within an uncertainty of 1% for both models. Both models fit the measured O2 and CO mixing ratios, the O3 abundance, and the O2 1.27-micrometer dayglow almost within the uncertainties of the measured values, though the model without nitrogen chemistry fits better. The importance of nitrogen chemistry in the lower and middle atmosphere of Mars depends on a fine balance between production of NO and N in the upper atmosphere which is not known within the required accuracy.

Exploration Of `Click' Chemistry For Microelectronic Applications

NASA Astrophysics Data System (ADS)

Musa, Osama M.; Sridhar, Laxmisha M.

The ‘Click’ chemistry was explored for low temperature snap cure and for possible use as an adhesion promoter in electronic applications. Several azide and alkyne resins were synthesized and their curing potential was evaluated with a special emphasis on exploring Cu(I) catalyst effect. The preliminary curing study in the absence of catalysts showed a strong dependence of cure temperatures on the electronic nature of alkynes. The cure temperatures showed a tendency to increase with decreasing electronegativity of the substituent on alkynes. The capability of Cu(I) catalysts to accelerate the ‘Click’ chemistry was demonstrated for the first time in bulk phase. Using several Cu(I) catalysts, the cure temperatures could be lowered by as much as 40-100°C compared to the control, depending on the nature of catalyst and the catalyst loading. We discovered a novel synergistic effect between Cu(I) and silver filler in lowering the cure temperatures. Using this combination, lower cure temperatures could be obtained than using either alone. Among several resins screened, one resin system has shown promise for 80°C snap-cure in which the aforementioned synergistic effect is operative. Solution phase ‘Click’ chemistry was employed for the synthesis of a hybrid triazole-epoxy resin system. This system was found to cure without added amine curative. The triazole group here serves as a linker as well as an internal adhesion promoter. To address the incompatibility and volatility issues, which arose during evaluation, a controlled oligomerization method has been developed using controlled heating of azides and alkynes in solution phase.

The effect of dissolution of volcanic glass on the water chemistry in a tuffaceous aquifer, Rainier Mesa, Nevada

USGS Publications Warehouse

White, Art F.; Claassen, H.C.; Benson, Larry V.

1980-01-01

Geochemistry of ground water associated with the Tertiary tuffs within Rainier Mesa, southern Nevada, was investigated to determine the relative importance of glass dissolution in controlling water chemistry. Water samples were obtained both from interstitial pores in core sections and from free-flowing fractures. Cation com- positions showed that calcium and magnesium decreased as a function of depth in the mesa, as sodium increased. The maximum effect occurs within alteration zones containing clinoptilolite and montmorillonite, suggesting these minerals effectively remove bivalent cations from the system. Comparisons are made between compositions of ground waters found within Rainier Mesa that apparently have not reacted with secondary minerals and compositions of waters produced by experimental dissolution of vitric and crystalline tufts which comprise the principal aquifers in the area. The two tuff phases have the same bulk chemistry but produce aqueous solutions of different chemistry. Rapid parabolic dissolution of sodium and silica from, and the retention of, potassium within the vitric phase verify previous predictions concerning water compositions associated with vitric volcanic rocks. Parabolic dissolution of the crystalline phase results in solutions high in calcium and magnesium and low in silica. Extrapolation of the parabolic dissolution mechanism for the vitric tuff to long times successfully reproduces, at com- parable pH, cation ratios existing in Rainier Mesa ground water. Comparison of mass- transfer rates of the vitric and crystalline tuffs indicates that the apparent higher glass-surface to aqueous-volume ratio associated with the vitric rocks may account for dominance of the glass reaction.

Beyond temperature: Clumped isotope signatures in dissolved inorganic carbon species and the influence of solution chemistry on carbonate mineral composition

NASA Astrophysics Data System (ADS)

Tripati, Aradhna K.; Hill, Pamela S.; Eagle, Robert A.; Mosenfelder, Jed L.; Tang, Jianwu; Schauble, Edwin A.; Eiler, John M.; Zeebe, Richard E.; Uchikawa, Joji; Coplen, Tyler B.; Ries, Justin B.; Henry, Drew

2015-10-01

;Clumped-isotope; thermometry is an emerging tool to probe the temperature history of surface and subsurface environments based on measurements of the proportion of 13C and 18O isotopes bound to each other within carbonate minerals in 13C18O16O22- groups (heavy isotope ;clumps;). Although most clumped isotope geothermometry implicitly presumes carbonate crystals have attained lattice equilibrium (i.e., thermodynamic equilibrium for a mineral, which is independent of solution chemistry), several factors other than temperature, including dissolved inorganic carbon (DIC) speciation may influence mineral isotopic signatures. Therefore we used a combination of approaches to understand the potential influence of different variables on the clumped isotope (and oxygen isotope) composition of minerals. We conducted witherite precipitation experiments at a single temperature and at varied pH to empirically determine 13C-18O bond ordering (Δ47) and δ18O of CO32- and HCO3- molecules at a 25 °C equilibrium. Ab initio cluster models based on density functional theory were used to predict equilibrium 13C-18O bond abundances and δ18O of different DIC species and minerals as a function of temperature. Experiments and theory indicate Δ47 and δ18O compositions of CO32- and HCO3- ions are significantly different from each other. Experiments constrain the Δ47-δ18O slope for a pH effect (0.011 ± 0.001; 12 ⩾ pH ⩾ 7). Rapidly-growing temperate corals exhibit disequilibrium mineral isotopic signatures with a Δ47-δ18O slope of 0.011 ± 0.003, consistent with a pH effect. Our theoretical calculations for carbonate minerals indicate equilibrium lattice calcite values for Δ47 and δ18O are intermediate between HCO3- and CO32-. We analyzed synthetic calcites grown at temperatures ranging from 0.5 to 50 °C with and without the enzyme carbonic anhydrase present. This enzyme catalyzes oxygen isotopic exchange between DIC species and is present in many natural systems. The two types of experiments yielded statistically indistinguishable results, and these measurements yield a calibration that overlaps with our theoretical predictions for calcite at equilibrium. The slow-growing Devils Hole calcite exhibits Δ47 and δ18O values consistent with lattice equilibrium. Factors influencing DIC speciation (pH, salinity) and the timescale for DIC equilibration, as well as reactions at the mineral-solution interface, have the potential to influence clumped-isotope signatures and the δ18O of carbonate minerals. In fast-growing carbonate minerals, solution chemistry may be an important factor, particularly over extremes of pH and salinity. If a crystal grows too rapidly to reach an internal equilibrium (i.e., achieve the value for the temperature-dependent mineral lattice equilibrium), it may record the clumped-isotope signature of a DIC species (e.g., the temperature-dependent equilibrium of HCO3-) or a mixture of DIC species, and hence record a disequilibrium mineral composition. For extremely slow-growing crystals, and for rapidly-grown samples grown at a pH where HCO3- dominates the DIC pool at equilibrium, effects of solution chemistry are likely to be relatively small or negligible. In summary, growth environment, solution chemistry, surface equilibria, and precipitation rate may all play a role in dictating whether a crystal achieves equilibrium or disequilibrium clumped-isotope signatures.

Questa baseline and pre-mining ground-water quality investigation. 20. Water chemistry of the Red River and selected seeps, tributaries, and precipitation, Taos County, New Mexico, 2000-2004

USGS Publications Warehouse

Verplanck, P.L.; McCleskey, R. Blaine; Nordstrom, D. Kirk

2006-01-01

As part of a multi-year project to infer the pre-mining ground-water quality at Molycorp's Questa mine site, surface-water samples of the Red River, some of its tributaries, seeps, and snow samples were collected for analysis of inorganic solutes and of water and sulfate stable isotopes in selected samples. The primary aim of this study was to document diel, storm event, and seasonal variations in water chemistry for the Red River and similar variations in water chemistry for Straight Creek, a natural analog site similar in topography, hydrology, and geology to the mine site for inferring pre-mining water-quality conditions. Red River water samples collected between 2000 and 2004 show that the largest variations in water chemistry occur during late summer rainstorms, often monsoonal in nature. Within hours, discharge of the Red River increased from 8 to 102 cubic feet per second and pH decreased from 7.80 to 4.83. The highest concentrations of metals (iron, aluminum, zinc, manganese) and sulfate also occur during such events. Low-pH and high-solute concentrations during rainstorm runoff are derived primarily from alteration 'scar' areas of naturally high mineralization combined with steep topography that exposes continually altered rock because erosion is too rapid for vegetative growth. The year 2002 was one of the driest on record, and Red River discharge reflected the low seasonal snow pack. No snowmelt peak appeared in the hydrograph record, and a late summer storm produced the highest flow for the year. Snowmelt was closer to normal during 2003 and demonstrated the dilution effect of snowmelt on water chemistry. Two diel sampling events were conducted for the Red River, one during low flow and the other during high flow, at two locations, at the Red River gaging station and just upstream from Molycorp's mill site. No discernible diel trends were observed except for dissolved zinc and manganese at the upstream site during low flow. Straight Creek drainage water was sampled periodically from 2001 to 2004 at the down stream end of surface drainage near the point at which it disappeared into the debris fan. This water has a minimal range in pH (2.7 to 3.2) but a substantial concentration range in many solutes; for example, sulfate concentrations varied from 525 to 2,660 mg/L. Many elements covary with sulfate suggesting that dilution is the primary control of the range in solute concentrations. A transect of water samples higher in the scar area were collected in October of 2003. They had a lower range in pH (2.44 to 3.05) and higher solute concentrations than those collected periodically from lower in the catchment. Water isotopes for the upper transect samples indicated slight evaporation, and in part, may account for the higher solute concentrations. Drainage waters also were collected from Hottentot, Junebug, Hansen, Little Hansen, and Goat Hill Gulch drainages. Most constituents from other scar drainage waters showed ranges of concentration similar to those of the Straight Creek waters. An exception was water collected from Goat Hill Gulch, which has some of the highest concentrations of any surface-water sample collected but also contained waste-rock leachates.

Beyond temperature: Clumped isotope signatures in dissolved inorganic carbon species and the influence of solution chemistry on carbonate mineral composition

USGS Publications Warehouse

Tripati, Aradhna K.; Hill, Pamela S.; Eagle, Robert A.; Mosenfelder, Jed L.; Tang, Jianwu; Schauble, Edwin A.; Eiler, John M.; Zeebe, Richard E.; Uchikawa, Joji; Coplen, Tyler B.; Ries, Justin B.; Henry, Drew

2015-01-01

“Clumped-isotope” thermometry is an emerging tool to probe the temperature history of surface and subsurface environments based on measurements of the proportion of 13C and 18O isotopes bound to each other within carbonate minerals in 13C18O16O22- groups (heavy isotope “clumps”). Although most clumped isotope geothermometry implicitly presumes carbonate crystals have attained lattice equilibrium (i.e., thermodynamic equilibrium for a mineral, which is independent of solution chemistry), several factors other than temperature, including dissolved inorganic carbon (DIC) speciation may influence mineral isotopic signatures. Therefore we used a combination of approaches to understand the potential influence of different variables on the clumped isotope (and oxygen isotope) composition of minerals.We conducted witherite precipitation experiments at a single temperature and at varied pH to empirically determine 13C-18O bond ordering (Δ47) and δ18O of CO32- and HCO3- molecules at a 25 °C equilibrium. Ab initio cluster models based on density functional theory were used to predict equilibrium 13C-18O bond abundances and δ18O of different DIC species and minerals as a function of temperature. Experiments and theory indicate Δ47 and δ18O compositions of CO32- and HCO3- ions are significantly different from each other. Experiments constrain the Δ47-δ18O slope for a pH effect (0.011 ± 0.001; 12 ⩾ pH ⩾ 7). Rapidly-growing temperate corals exhibit disequilibrium mineral isotopic signatures with a Δ47-δ18O slope of 0.011 ± 0.003, consistent with a pH effect.Our theoretical calculations for carbonate minerals indicate equilibrium lattice calcite values for Δ47 and δ18O are intermediate between HCO3− and CO32−. We analyzed synthetic calcites grown at temperatures ranging from 0.5 to 50 °C with and without the enzyme carbonic anhydrase present. This enzyme catalyzes oxygen isotopic exchange between DIC species and is present in many natural systems. The two types of experiments yielded statistically indistinguishable results, and these measurements yield a calibration that overlaps with our theoretical predictions for calcite at equilibrium. The slow-growing Devils Hole calcite exhibits Δ47 and δ18O values consistent with lattice equilibrium.Factors influencing DIC speciation (pH, salinity) and the timescale for DIC equilibration, as well as reactions at the mineral–solution interface, have the potential to influence clumped-isotope signatures and the δ18O of carbonate minerals. In fast-growing carbonate minerals, solution chemistry may be an important factor, particularly over extremes of pH and salinity. If a crystal grows too rapidly to reach an internal equilibrium (i.e., achieve the value for the temperature-dependent mineral lattice equilibrium), it may record the clumped-isotope signature of a DIC species (e.g., the temperature-dependent equilibrium of HCO3−) or a mixture of DIC species, and hence record a disequilibrium mineral composition. For extremely slow-growing crystals, and for rapidly-grown samples grown at a pH where HCO3- dominates the DIC pool at equilibrium, effects of solution chemistry are likely to be relatively small or negligible. In summary, growth environment, solution chemistry, surface equilibria, and precipitation rate may all play a role in dictating whether a crystal achieves equilibrium or disequilibrium clumped-isotope signatures.

Photochemical organic oxidations and dechlorinations with a mu-oxo bridged heme/non-heme diiron complex.

PubMed

Wasser, Ian M; Fry, H Christopher; Hoertz, Paul G; Meyer, Gerald J; Karlin, Kenneth D

2004-12-27

Steady state and laser flash photolysis studies of the heme/non-heme mu-oxo diiron complex [((6)L)Fe(III)-O-Fe(III)-Cl](+) (1) have been undertaken. The anaerobic photolysis of benzene solutions of 1 did not result in the buildup of any photoproduct. However, the addition of excess triphenylphosphine resulted in the quantitative photoreduction of 1 to [((6)L)Fe(II)...Fe(II)-Cl](+) (2), with concomitant production by oxo-transfer of 1 equiv of triphenylphosphine oxide. Under aerobic conditions and excess triphenylphosphine, the reaction produces multiple turnovers (approximately 28) before the diiron complex is degraded. The anaerobic photolysis of tetrahydrofuran (THF) or toluene solutions of 1 likewise results in the buildup of 2. The oxidation products from these reactions included gamma-butyrolactone (approximately 15%) for the reaction in THF and benzaldehyde (approximately 23%) from the reaction in toluene. In either case, the O-atom which is incorporated into the carbonyl product is derived from dioxygen present under workup or under aerobic photolysis conditions. Transient absorption measurements of low-temperature THF solutions of 1 revealed the presence of an (P)Fe(II)-like [P = tetraaryl porphyrinate dianion] species suggesting that the reactive species is a formal (heme)Fe(II)/Fe(IV)=O(non-heme) pair. The non-heme Fe(IV)=O is thus most likely responsible for C-H bond cleavage and subsequent radical chemistry. The photolysis of 1 in chlorobenzene or 1,2-dichlorobenzene resulted in C-Cl cleavage reactions and the formation of [[((6)L)Fe(III)-Cl...Fe(III)-Cl](2)O](2+) (3), with chloride ligands that are derived from solvent dehalogenation chemistry. The resulting organic products are biphenyl trichlorides or biphenyl monochlorides, derived from dichlorobenzene and chlorobenzene, respectively. Similarly, product 3 is obtained by the photolysis of benzene-benzyl chloride solutions of 1; the organic product is benzaldehyde (approximately 70%). A brief discussion of the dehalogenation chemistry, along with relevant environmental perspectives, is included.

Enhancing chemistry problem-solving achievement using problem categorization

NASA Astrophysics Data System (ADS)

Bunce, Diane M.; Gabel, Dorothy L.; Samuel, John V.

The enhancement of chemistry students' skill in problem solving through problem categorization is the focus of this study. Twenty-four students in a freshman chemistry course for health professionals are taught how to solve problems using the explicit method of problem solving (EMPS) (Bunce & Heikkinen, 1986). The EMPS is an organized approach to problem analysis which includes encoding the information given in a problem (Given, Asked For), relating this to what is already in long-term memory (Recall), and planning a solution (Overall Plan) before a mathematical solution is attempted. In addition to the EMPS training, treatment students receive three 40-minute sessions following achievement tests in which they are taught how to categorize problems. Control students use this time to review the EMPS solutions of test questions. Although problem categorization is involved in one section of the EMPS (Recall), treatment students who received specific training in problem categorization demonstrate significantly higher achievement on combination problems (those problems requiring the use of more than one chemical topic for their solution) at (p = 0.01) than their counterparts. Significantly higher achievement for treatment students is also measured on an unannounced test (p = 0.02). Analysis of interview transcripts of both treatment and control students illustrates a Rolodex approach to problem solving employed by all students in this study. The Rolodex approach involves organizing equations used to solve problems on mental index cards and flipping through them, matching units given when a new problem is to be solved. A second phenomenon observed during student interviews is the absence of a link in the conceptual understanding of the chemical concepts involved in a problem and the problem-solving skills employed to correctly solve problems. This study shows that explicit training in categorization skills and the EMPS can lead to higher achievement in complex problem-solving situations (combination problems and unannounced test). However, such achievement may be limited by the lack of linkages between students' conceptual understanding and improved problem-solving skill.

Solvophobic and solvophilic contributions in the water-to-aqueous guanidinium chloride transfer free energy of model peptides

NASA Astrophysics Data System (ADS)

Tomar, Dheeraj S.; Ramesh, Niral; Asthagiri, D.

2018-06-01

We study the solvation free energy of two different conformations (helix and extended) of two different peptides (deca-alanine and deca-glycine) in two different solvents (water and aqueous guanidinium chloride, GdmCl). The free energies are obtained using the quasichemical organization of the potential distribution theorem, an approach that naturally provides the repulsive (solvophobic or cavity) and attractive (solvophilic) contributions to solvation. The solvophilic contribution is further parsed into a chemistry contribution arising from solute interaction with the solvent in the first solvation shell and a long-range contribution arising from non-specific interactions between the solute and the solvent beyond the first solvation shell. The cavity contribution is obtained for two different envelopes, ΣS E, which theory helps identify as the solvent excluded volume, and ΣG, a larger envelope beyond which solute-solvent interactions are Gaussian. The ΣS E envelope is independent of the solvent, as expected on the basis of the insensitivity to the solvent type of the distance of closest approach between protein heavy atoms and solvent heavy atoms, but contrary to the intuition based on treating solvent constituents as spheres of some effective radii. For both envelopes, the cavity contribution in water is proportional to the surface area of the envelope. The same does not hold for GdmCl(aq), revealing the limitation of using molecular area to assess solvation energetics. The ΣG-cavity contribution predicts that GdmCl(aq) should favor the more compact state, contrary to the role of GdmCl in unfolding proteins. The chemistry contribution attenuates this effect, but still the net local (chemistry plus ΣG-packing) contribution is inadequate in capturing the role of GdmCl. With the inclusion of the long-range contribution, which is dominated by van der Waals interaction, aqueous GdmCl favors the extended conformation over the compact conformation. Our finding emphasizes the importance of weak, but attractive, long-range dispersion interactions in protein solution thermodynamics.

Solvophobic and solvophilic contributions in the water-to-aqueous guanidinium chloride transfer free energy of model peptides.

PubMed

Tomar, Dheeraj S; Ramesh, Niral; Asthagiri, D

2018-06-14

We study the solvation free energy of two different conformations (helix and extended) of two different peptides (deca-alanine and deca-glycine) in two different solvents (water and aqueous guanidinium chloride, GdmCl). The free energies are obtained using the quasichemical organization of the potential distribution theorem, an approach that naturally provides the repulsive (solvophobic or cavity) and attractive (solvophilic) contributions to solvation. The solvophilic contribution is further parsed into a chemistry contribution arising from solute interaction with the solvent in the first solvation shell and a long-range contribution arising from non-specific interactions between the solute and the solvent beyond the first solvation shell. The cavity contribution is obtained for two different envelopes, Σ SE , which theory helps identify as the solvent excluded volume, and Σ G , a larger envelope beyond which solute-solvent interactions are Gaussian. The Σ SE envelope is independent of the solvent, as expected on the basis of the insensitivity to the solvent type of the distance of closest approach between protein heavy atoms and solvent heavy atoms, but contrary to the intuition based on treating solvent constituents as spheres of some effective radii. For both envelopes, the cavity contribution in water is proportional to the surface area of the envelope. The same does not hold for GdmCl(aq), revealing the limitation of using molecular area to assess solvation energetics. The Σ G -cavity contribution predicts that GdmCl(aq) should favor the more compact state, contrary to the role of GdmCl in unfolding proteins. The chemistry contribution attenuates this effect, but still the net local (chemistry plus Σ G -packing) contribution is inadequate in capturing the role of GdmCl. With the inclusion of the long-range contribution, which is dominated by van der Waals interaction, aqueous GdmCl favors the extended conformation over the compact conformation. Our finding emphasizes the importance of weak, but attractive, long-range dispersion interactions in protein solution thermodynamics.

Adhesion of bacterial pathogens to soil colloidal particles: influences of cell type, natural organic matter, and solution chemistry.

PubMed

Zhao, Wenqiang; Walker, Sharon L; Huang, Qiaoyun; Cai, Peng

2014-04-15

Bacterial adhesion to granular soil particles is well studied; however, pathogen interactions with naturally occurring colloidal particles (<2 μm) in soil has not been investigated. This study was developed to identify the interaction mechanisms between model bacterial pathogens and soil colloids as a function of cell type, natural organic matter (NOM), and solution chemistry. Specifically, batch adhesion experiments were conducted using NOM-present, NOM-stripped soil colloids, Streptococcus suis SC05 and Escherichia coli WH09 over a wide range of solution pH (4.0-9.0) and ionic strength (IS, 1-100 mM KCl). Cell characterization techniques, Freundlich isotherm, and Derjaguin-Landau-Verwey-Overbeek (DLVO) theory (sphere-sphere model) were utilized to quantitatively determine the interactions between cells and colloids. The adhesion coefficients (Kf) of S. suis SC05 to NOM-present and NOM-stripped soil colloids were significantly higher than E. coli WH09, respectively. Similarly, Kf values of S. suis SC05 and E. coli WH09 adhesion to NOM-stripped soil colloids were greater than those colloids with NOM-present, respectively, suggesting NOM inhibits bacterial adhesion. Cell adhesion to soil colloids declined with increasing pH and enhanced with rising IS (1-50 mM). Interaction energy calculations indicate these adhesion trends can be explained by DLVO-type forces, with S. suis SC05 and E. coli WH09 being weakly adhered in shallow secondary energy minima via polymer bridging and charge heterogeneity. S. suis SC05 adhesion decreased at higher IS 100 mM, which is attributed to the change of hydrophobic effect and steric repulsion resulted from the greater presence of extracellular polymeric substances (EPS) on S. suis SC05 surface as compared to E. coli WH09. Hence, pathogen adhesion to the colloidal material is determined by a combination of DLVO, charge heterogeneity, hydrophobic and polymer interactions as a function of solution chemistry. Copyright © 2014 Elsevier Ltd. All rights reserved.

Halogen bonding in solution: thermodynamics and applications.

PubMed

Beale, Thomas M; Chudzinski, Michael G; Sarwar, Mohammed G; Taylor, Mark S

2013-02-21

Halogen bonds are noncovalent interactions in which covalently bound halogens act as electrophilic species. The utility of halogen bonding for controlling self-assembly in the solid state is evident from a broad spectrum of applications in crystal engineering and materials science. Until recently, it has been less clear whether, and to what extent, halogen bonding could be employed to influence conformation, binding or reactivity in the solution phase. This tutorial review summarizes and interprets solution-phase thermodynamic data for halogen bonding interactions obtained over the past six decades and highlights emerging applications in molecular recognition, medicinal chemistry and catalysis.

Silver Trees: Chemistry on a TEM Grid

EPA Science Inventory

The copper/carbon substrate of a TEM grid reacted with aqueous silver nitrate solution within minutes to yield spectacular tree-like silver dendrites, without using any added capping or reducing reagents. These results demonstrate a facile, aqueous, room temperature synthesis of...

Chemical Compound Design Using Nuclear Charge Distributions

DTIC Science & Technology

2012-03-01

Finding optimal solutions to design problems in chemistry is hampered by the combinatorially large search space. We develop a general theoretical ... framework for finding chemical compounds with prescribed properties using nuclear charge distributions. The key is the reformulation of the design

Chemistry Notes.

ERIC Educational Resources Information Center

School Science Review, 1984

1984-01-01

Presents an experiment which links mass spectrometry to gas chromatography. Also presents a simulation of iron extraction using a ZX81 computer and discussions of Fehling versus Benedict's solutions, transition metal ammine complexes, electrochemical and other chemical series, and a simple model of dynamic equilibria. (JN)

Mineralogy and geochemistry of efflorescent minerals on mine tailings and their potential impact on water chemistry.

PubMed

Grover, B P C; Johnson, R H; Billing, D G; Weiersbye, I M G; Tutu, H

2016-04-01

In the gold mining Witwatersrand Basin of South Africa, efflorescent mineral crusts are a common occurrence on and nearby tailings dumps during the dry season. The crusts are readily soluble and generate acidic, metal- and sulphate-rich solutions on dissolution. In this study, the metal content of efflorescent crusts at an abandoned gold mine tailings dump was used to characterise surface and groundwater discharges from the site. Geochemical modelling of the pH of the solution resulting from the dissolution of the crusts was used to better understand the crusts' potential impact on water chemistry. The study involved two approaches: (i) conducting leaching experiments on oxidised and unoxidised tailings using artificial rainwater and dilute sulphuric acid and correlating the composition of crusts to these leachates and (ii) modelling the dissolution of the crusts in order to gain insight into their mineralogy and their potential impact on receiving waters. The findings suggested that there were two chemically distinct discharges from the site, namely an aluminium- and magnesium-rich surface water plume and an iron-rich groundwater plume. The first plume was observed to originate from the oxidised tailings following leaching with rainwater while the second plume originated from the underlying unoxidised tailings with leaching by sulphuric acid. Both groups of minerals forming from the respective plumes were found to significantly lower the pH of the receiving water with simulations of their dissolution found to be within 0.2 pH units of experimental values. It was observed that metals in a low abundance within the crust (for example, iron) had a stronger influence on the pH of the resulting solutions than metals in a greater abundance (aluminium or magnesium). Techniques such as powder X-ray diffraction (PXRD) and in situ mineral determination techniques such as remote sensing can effectively determine the dominant mineralogy. However, the minerals or metals incorporated through solid solution into bulk mineralogy that dominates the chemistry of the solutions upon their dissolution may occur in minor quantities that can only be predicted using chemical analysis. Their mineralogy can be predicted using geochemical modelling and can provide a set of hypothetical minerals that upon dissolution yield a solution similar to that of the actual crusts. This realisation has a bearing on decision-making such as in risk assessment and designing pollutant mitigation strategies.

Towards medicinal mechanochemistry: evolution of milling from pharmaceutical solid form screening to the synthesis of active pharmaceutical ingredients (APIs).

PubMed

Tan, Davin; Loots, Leigh; Friščić, Tomislav

2016-06-14

This overview highlights the emergent area of mechanochemical reactions for making active pharmaceutical ingredients (APIs), and covers the latest advances in the recently established area of mechanochemical screening and synthesis of pharmaceutical solid forms, specifically polymorphs, cocrystals, salts and salt cocrystals. We also provide an overview of the most recent developments in pharmaceutical uses of mechanochemistry, including real-time reaction monitoring, techniques for polymorph control and approaches for continuous manufacture using twin screw extrusion, and more. Most importantly, we show how the overlap of previously unrelated areas of mechanochemical screening for API solid forms, organic synthesis by milling, and mechanochemical screening for molecular recognition, enables the emergence of a new research discipline in which different aspects of pharmaceutical and medicinal chemistry are addressed through mechanochemistry rather than through conventional solution-based routes. The emergence of such medicinal mechanochemistry is likely to have a strong impact on future pharmaceutical and medicinal chemistry, as it offers not only access to materials and reactivity that are sometimes difficult or even impossible to access from solution, but can also provide a general answer to the demands of the pharmaceutical industry for cleaner, safer and efficient synthetic solutions.

Effect of Ionic Strength and Surface Charge Density on the Kinetics of Cellulose Nanocrystal Thin Film Swelling.

PubMed

Reid, Michael S; Kedzior, Stephanie A; Villalobos, Marco; Cranston, Emily D

2017-08-01

This work explores cellulose nanocrystal (CNC) thin films (<50 nm) and particle-particle interactions by investigating film swelling in aqueous solutions with varying ionic strength (1-100 mM). CNC film hydration was monitored in situ via surface plasmon resonance, and the kinetics of liquid uptake were quantified. The contribution of electrostatic double-layer forces to film swelling was elucidated by using CNCs with different surface charges (anionic sulfate half ester groups, high and low surface charge density, and cationic trimethylammonium groups). Total water uptake in the thin films was found to be independent of ionic strength and surface chemistry, suggesting that in the aggregated state van der Waals forces dominate over double-layer forces to hold the films together. However, the rate of swelling varied significantly. The water uptake followed Fickian behavior, and the measured diffusion constants decreased with the ionic strength gradient between the film and the solution. This work highlights that nanoparticle interactions and dispersion are highly dependent on the state of particle aggregation and that the rate of water uptake in aggregates and thin films can be tailored based on surface chemistry and solution ionic strength.

Occupational safety and health, green chemistry, and sustainability: a review of areas of convergence.

PubMed

Schulte, Paul A; McKernan, Lauralynn T; Heidel, Donna S; Okun, Andrea H; Dotson, Gary Scott; Lentz, Thomas J; Geraci, Charles L; Heckel, Pamela E; Branche, Christine M

2013-04-15

With increasing numbers and quantities of chemicals in commerce and use, scientific attention continues to focus on the environmental and public health consequences of chemical production processes and exposures. Concerns about environmental stewardship have been gaining broader traction through emphases on sustainability and "green chemistry" principles. Occupational safety and health has not been fully promoted as a component of environmental sustainability. However, there is a natural convergence of green chemistry/sustainability and occupational safety and health efforts. Addressing both together can have a synergistic effect. Failure to promote this convergence could lead to increasing worker hazards and lack of support for sustainability efforts. The National Institute for Occupational Safety and Health has made a concerted effort involving multiple stakeholders to anticipate and identify potential hazards associated with sustainable practices and green jobs for workers. Examples of potential hazards are presented in case studies with suggested solutions such as implementing the hierarchy of controls and prevention through design principles in green chemistry and green building practices. Practical considerations and strategies for green chemistry, and environmental stewardship could benefit from the incorporation of occupational safety and health concepts which in turn protect affected workers.

Corrosion of titanium and zirconium in organic solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clapp, R.A.; Saldanha, B.J.; Kvochak, J.J.

1995-09-01

Experiences of reactive metal corrosion in organic acids will be discussed. Emphasis will be placed on anhydrous organic solutions, and organic acids containing halides which are often added as catalysts or promoters. The case examples will illustrate the importance of evaluating reactive metals under conditions that closely simulate actual process chemistry, type of exposure (vapor, liquid, condensate), and final fabricated form, to ensure that the material will provide predictable long-term service in a commercial facility.

Undergraduate Analytical Chemistry Experiment: The Determination of Formation Constants for Acetate and Mono-and Dichloroacetate Salts of Primary, Secondary, and Tertiary Methyl-and Ethylamines

ERIC Educational Resources Information Center

D'Amelia, Ronald P.; Chiang, Stephanie; Pollut, Stephanie; Nirode, William F.

2014-01-01

The formation and the hydrolysis of organic salts produced by the titration of a 0.1 M solution of the following amines: methyl-, dimethyl-, trimethyl-, ethyl-, diethyl-, and triethylamine with a 0.1 M solution of acetic, chloroacetic, and dichloracetic acids are studied. The pK[subscript b] of the amine and the pH at the end point were determined…

Identifying the role of N-heteroatom location in the activity of metal catalysts for alcohol oxidation

DOE PAGES

Chan-Thaw, Carine E.; Veith, Gabriel M.; Villa, Alberto; ...

2015-04-02

Here, this work focuses on understanding how the bonding of nitrogen heteroatoms contained on/in a activated carbon support influence the stability and reactivity of a supported Pd catalyst for the oxidation of alcohols in solution. The results show that simply adding N groups via solution chemistry is insufficient to improve catalytic properties. Instead a strongly bound N moiety is required to activate the catalyst and stabilize the metal particles.

The Adsorption of Bromide Ion at Mercury from Propylene Carbonate Solutions of Constant Ionic Strength

DTIC Science & Technology

1991-05-20

Chemistry University of California Davis, CA 95616 * To whom correspondence should be addressed. t Permanent address: Instituto de Fisica e Quimica ...I]. In the case of Br- ion adsorption at Hg, studies have been carried out in water [2-4] and N- methylformamide solutions [5,6] of both varying and...discussed with respect to current theoretical developments. 4 Experimental Differential capacity against potential data were obtained for the mercury

A Designer Fluid For Aluminum Phase Change Devices: Aluminum Inorganic Aqueous Solutions (IAS) Chemistry and Experiments. Volume 2

DTIC Science & Technology

2016-11-17

magnitude larger than necessary. Adding more permanganate into the solution can produce a thicker coating . Manganese oxide has a thermal conductivity ...void before sealing both ends. For terrestrial heat pipes, copper is the most commonly used casing material due to its high thermal conductivity ... thermal conductivity ; however, these were early results and the tubes that were obtained from the Chinese manufacturer appeared to be of inconsistent

Experiments on the Multiphase Chemistry of Isocyanic Acid, HNCO.

NASA Astrophysics Data System (ADS)

Roberts, J. M.; Liu, Y.

2015-12-01

Isocyanic acid, HNCO, has emerged as a potentially important reduced nitrogen compound that is emitted in wildfires, and may have health effect implications. The extent of the health effects depends on the solubility of HNCO in aqueous and non-aqueous solutions and the relative rates of hydrolysis versus carbamylation reactions (for example: HNCO + ROH => H2NC(O)OR). We report here results of studies of HNCO solubility and its reaction in buffered aqueous solutions (pH3), tridecane, and n-octanol at temperatures over the range 5 to 37°C. From these data, the heats of solution and activation energy of hydrolysis are estimated, and a partition coefficient between n-octanol and water at 25°C is greater than 1 for low pH solutions, indicating appreciable portioning to a non-polar phase, but HNCO will be distributed mostly in the aqueous phase at neutral pH. In addition, it was found that the rate of reaction of HNCO with n-octanol was competitive with hydrolysis under physiologically relevant conditions (pH7.4, 37°C), indicating that carbamylation of ROH groups could be significant. Based on these results, research on the carbamylation of other functional groups, and solubility and reaction studies of other isocyanates (e.g. CH3NCO) are warranted. The implications of this multi-phase chemistry for global exposures to wildfire emissions will be discussed.

Modular syntheses of H₄octapa and H₂dedpa, and yttrium coordination chemistry relevant to ⁸⁶Y/⁹⁰Y radiopharmaceuticals.

PubMed

Price, Eric W; Cawthray, Jacqueline F; Adam, Michael J; Orvig, Chris

2014-05-21

The ligands H2dedpa, H4octapa, p-SCN-Bn-H2dedpa, and p-SCN-Bn-H4octapa were synthesized using a new protection chemistry approach, with labile tert-butyl esters replacing the previously used methyl esters as protecting groups for picolinic acid moieties. Additionally, the ligands H2dedpa and p-SCN-Bn-H2dedpa were synthesized using nosyl protection chemistry for the first time. The use of tert-butyl esters allows for deprotection at room temperature in trifluoroacetic acid (TFA), which compares favorably to the harsh conditions of refluxing HCl (6 M) or LiOH that were previously required for methyl ester cleavage. H4octapa has recently been shown to be a very promising (111)In and (177)Lu ligand for radiopharmaceutical applications; therefore, coordination chemistry studies with Y(3+) are described to assess its potential for use with (86)Y/(90)Y. The solution chemistry of H4octapa with Y(3+) is shown to be suitable via solution NMR studies of the [Y(octapa)](-) complex and density functional theory (DFT) calculations of the predicted structure, suggesting properties similar to those of the analogous In(3+) and Lu(3+) complexes. The molecular electrostatic potential (MEP) was mapped onto the molecular surface of the DFT-calculated coordination structures, suggesting very similar and even charge distributions between both the Lu(3+) and Y(3+) complexes of octapa(4-), and coordinate structures between 8 (ligand only) and 9 (ligand and one H2O). Potentiometric titrations determined H4octapa to have a formation constant (log K(ML)) with Y(3+) of 18.3 ± 0.1, revealing high thermodynamic stability. This preliminary work suggests that H4octapa may be a competent ligand for future (86)Y/(90)Y radiopharmaceutical applications.

Thermal properties of spinel based solid solutions

NASA Astrophysics Data System (ADS)

O'Hara, Kelley Rae

Solid solution formation in spinel based systems proved to be a viable approach to decreasing thermal conductivity. Samples with systematically varied additions of MgGa2O4 to MgAl2O 4 were prepared and thermal diffusivity was measured using the laser flash technique. Additionally, heat capacity was measured using differential scanning calorimetry and modeled for the MgAl2O4-MgGa 2O4 system. At 200°C thermal conductivity decreased 24% with a 5 mol% addition of MgGa2O4 to the system. The solid solution continued to decrease the thermal conductivity by 13% up to 1000°C with 5 mol% addition. The decrease in thermal conductivity ultimately resulted in a decrease in heat flux when applied to a theoretical furnace lining, which could lead to energy savings in industrial settings. The MgAl2O4-Al2O3 phase equilibria was investigated to fully understand the system and the thermal properties at elevated temperatures. The solvus line between MgAl2O4 and Al2O3 has been defined at 79.6 wt% Al 2O3 at 1500°C, 83.0 wt% Al2O4 at 1600°C, and 86.5 wt% Al2O3 at 1700°C. A metastable region has been identified at temperatures up to 1700°C which could have significant implications for material processing and properties. The spinel solid solution region has been extended to form an infinite solid solution with Al2O3 at elevated temperatures. A minimum in melting at 1975°C and a chemistry of 96 wt% Al2O3 rather than a eutectic is present. Thermal properties in the MgAl2O4-Al2O 3 system were investigated in both the single phase solid solution region and the two phase region. The thermal diffusivity decreased through the MgAl 2O4 solid solution region and was at a minimum through the entire metastable (nucleation and growth) region. As Al2O 3 became present as a second phase the thermal diffusivity increased with Al2O3 content. There was an 11.7% increase in thermal diffusivity with a change in overall chemistry of 85.20 wt% Al2O 3 to 87.71 wt% Al2O3, due to the drastic change in final chemistry (38.3 wt% Al20 3) caused by the nucleation and growth region in the system.

Covalent-Bond Formation via On-Surface Chemistry.

PubMed

Held, Philipp Alexander; Fuchs, Harald; Studer, Armido

2017-05-02

In this Review article pioneering work and recent achievements in the emerging research area of on-surface chemistry is discussed. On-surface chemistry, sometimes also called two-dimensional chemistry, shows great potential for bottom-up preparation of defined nanostructures. In contrast to traditional organic synthesis, where reactions are generally conducted in well-defined reaction flasks in solution, on-surface chemistry is performed in the cavity of a scanning probe microscope on a metal crystal under ultrahigh vacuum conditions. The metal first acts as a platform for self-assembly of the organic building blocks and in many cases it also acts as a catalyst for the given chemical transformation. Products and hence success of the reaction are directly analyzed by scanning probe microscopy. This Review provides a general overview of this chemistry highlighting advantages and disadvantages as compared to traditional reaction setups. The second part of the Review then focuses on reactions that have been successfully conducted as on-surface processes. On-surface Ullmann and Glaser couplings are addressed. In addition, cyclodehydrogenation reactions and cycloadditions are discussed and reactions involving the carbonyl functionality are highlighted. Finally, the first examples of sequential on-surface chemistry are considered in which two different functionalities are chemoselectively addressed. The Review gives an overview for experts working in the area but also offers a starting point to non-experts to enter into this exciting new interdisciplinary research field. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemistry Notes

ERIC Educational Resources Information Center

School Science Review, 1972

1972-01-01

Short articles on the determination of the activation energy of the thiosulphate-acid reaction, an experiment on hydrolysis of similar metal salt solutions, the preparation and electrolytic properties of iodine monochloride and iodine trochloride, and instructions for apparatus enabling laboratory study of the thermal cracking of ethylbenzene. (AL)

Sleuthing the Nutrients that Make Your Houseplant Grow.

ERIC Educational Resources Information Center

Hershey, David R.

1990-01-01

Consumer chemistry projects using houseplant fertilizers are described. Background information on fertilizer elements and different brands are discussed. The procedures for the activities (reading fertilizer labels, calculating the cost of various fertilizers, and calculating the amount of nitrogen in solution) are included. (KR)

Macro Learning on a Micro Scale. Link Biology and Chemistry.

ERIC Educational Resources Information Center

Falk, Peter M.

1990-01-01

Described are several laboratory investigations that may be used to introduce biochemistry. Topics covered include carbohydrates, lipids, proteins, and metabolism. Reactions, stock solution formulas, and procedures are listed. Emphasized are individualizing work, designing alternative investigations, solving problems, and drawing conclusions. (KR)

Production of metals and compounds by radiation chemistry

NASA Technical Reports Server (NTRS)

Marsik, S. J.; Philipp, W. H.

1969-01-01

Preparation of metals and compounds by radiation induced chemical reactions involves irradiation of metal salt solutions with high energy electrons. This technique offers a method for the preparation of high purity metals with minimum contamination from the container material or the cover gas.

Collaboration across disciplines for sustainability: green chemistry as an emerging multistakeholder community.

PubMed

Iles, Alastair; Mulvihill, Martin J

2012-06-05

Sustainable solutions to our nation's material and energy needs must consider environmental, health, and social impacts while developing new technologies. Building a framework to support interdisciplinary interactions and incorporate sustainability goals into the research and development process will benefit green chemistry and other sciences. This paper explores the contributions that diverse disciplines can provide to the design of greener technologies. These interactions have the potential to create technologies that simultaneously minimize environmental and health impacts by drawing on the combined expertise of students and faculty in chemical sciences, engineering, environmental health, social sciences, public policy, and business.

Gamma irradiation of isocitric and citric acid in aqueous solution: Relevance in prebiotic chemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Negrón-Mendoza, A., E-mail: negron@nucleares.unam.mx; Ramos-Bernal, S.

The radiation chemistry of hydroxy acids like citric and isocitric acids is rather scarce, even though they are crucial compounds in biological systems and for food irradiation. The aim of this work is to study the radiolytic behavior of these acids focused on the interconversion induced by radiation of citric and isocitric acid into other members of the Krebs cycle. The results showed that among the products formed were succinic, malonic, malic and other acids related to metabolic pathways, and these results are correlated with its possible role in chemical evolution processes.

Polynuclear complexes of copper(I) halides: coordination chemistry and catalytic transformations of alkynes

NASA Astrophysics Data System (ADS)

Mykhalichko, B. M.; Temkin, Oleg N.; Mys'kiv, M. G.

2000-11-01

Characteristic features of the coordination chemistry of Cu(I) and mechanisms of catalytic conversions of alkynes in the CuCl-MCl-H2O-HC≡CR system (MCl is alkali metal or ammonium chloride or amine hydrochloride; R=H, CH2OH, CH=CH2, etc.) are analysed based on studies of the compositions and structures of copper(I) chloride (bromide) complexes, alkyne π-complexes and ethynyl organometallic polynuclear compounds formed in this system in solutions and in the crystalline state. The role of polynuclear complexes in various reactions of alkynes is discussed. The bibliography includes 149 references.

Quarterly progress report for the Chemical and Energy Research Section of the Chemical Technology Division, April--June 1997

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jubin, R.T.

The Chemical and Energy Research Section conducts basic and applied research and development in chemical engineering, applied chemistry, and bioprocessing, with an emphasis on energy-driven technologies and advanced chemical separations for nuclear and waste applications. The report describes the various tasks performed within six major areas of research: Hot Cell Operations, Process Chemistry and thermodynamics, Separations and Materials Synthesis, Solution Thermodynamics, biotechnology Research, and Molecular Studies. The name of a technical contact is included with each task described, and readers are encouraged to contact these individuals if they need additional information.

Reports of the second All-Union conference on the chemistry of transplutonium elements (Dmitrovgrad, June 21-23, 1963)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1987-05-01

The nine papers presented at this conference cover the following topics: the systematization, condensed description, and prediction of sets of anion exchange extraction constants on the basis of their statistical computer treatment; characteristics and uses of solid extractants containing D2EHPA and TBP for separating the transplutonium elements; enrichment of americium 242m and americium 242 by the Szilard-Chalmers method; an x-ray diffraction pattern analysis for transplutonium compounds; the radiation chemistry of americium; and the effects of alpha irradiation on the behavior of americium in perchlorate solutions.

A diagonal implicit scheme for computing flows with finite-rate chemistry

NASA Technical Reports Server (NTRS)

Eberhardt, Scott; Imlay, Scott

1990-01-01

A new algorithm for solving steady, finite-rate chemistry, flow problems is presented. The new scheme eliminates the expense of inverting large block matrices that arise when species conservation equations are introduced. The source Jacobian matrix is replaced by a diagonal matrix which is tailored to account for the fastest reactions in the chemical system. A point-implicit procedure is discussed and then the algorithm is included into the LU-SGS scheme. Solutions are presented for hypervelocity reentry and Hydrogen-Oxygen combustion. For the LU-SGS scheme a CFL number in excess of 10,000 has been achieved.

Significant alteration of Critical Zone processes in urban watersheds: shifting from a transport-limited to a weathering-limited regime

NASA Astrophysics Data System (ADS)

Moore, J.; Bird, D. L.; Dobbis, S. K.; Woodward, G.

2016-12-01

Urban areas and associated impervious surface cover (ISC) are among the fastest growing land use types. Rapid growth of urban lands has significant implications for geochemical cycling and solute sources to streams, estuaries, and coastal waters. However, little work has been done to investigate the impacts of urbanization on Critical Processes, including on the export of solutes from urban watersheds. Despite observed elevated solute concentrations in urban streams in some previous studies, neither solute sources nor total solute fluxes have been quantified due to mixed bedrock geology, lack of a forested reference watershed, or the presence of point sources that confounded separation of anthropologic and natural sources. We investigated the geochemical signal of the urban built environment (e.g., roads, parking lots, buildings) in a set of five USGS-gaged watersheds across a rural (forested) to urban gradient in the Maryland Piedmont. These watersheds have ISC ranging from 0 to 25%, no point sources, and similar felsic bedrock chemistry. Weathering from the urban built environment and ISC produces dramatically higher solute concentrations in urban watersheds than in the forested watershed. Higher solute concentrations result in chemical weathering fluxes from urban watersheds that are 11-13 times higher than the forested watershed and are similar to fluxes from mountainous, weathering-limited watersheds rather than fluxes from transport-limited, dilute streams like the forested watershed. Weathering of concrete in urban watersheds produces geochemistry similar to weathering-limited watersheds with high concentrations of Ca2+, Mg2+, and DIC, which is similar to stream chemistry due to carbonate weathering. Road salt dissolution results in high Na+ and Cl- concentrations similar to evaporite weathering. Quantifying processes causing elevated solute fluxes from urban areas is essential to understanding cycling of Ca2+, Mg2+, and DIC in urban streams and in downgradient estuarine or coastal waters.

Controls on soil solution nitrogen along an altitudinal gradient in the Scottish uplands.

PubMed

Jackson-Blake, L; Helliwell, R C; Britton, A J; Gibbs, S; Coull, M C; Dawson, L

2012-08-01

Nitrogen (N) deposition continues to threaten upland ecosystems, contributing to acidification, eutrophication and biodiversity loss. We present results from a monitoring study aimed at investigating the fate of this deposited N within a pristine catchment in the Cairngorm Mountains (Scotland). Six sites were established along an elevation gradient (486-908 m) spanning the key habitats of temperate maritime uplands. Bulk deposition chemistry, soil carbon content, soil solution chemistry, soil temperature and soil moisture content were monitored over a 5 year period. Results were used to assess spatial variability in soil solution N and to investigate the factors and processes driving this variability. Highest soil solution inorganic N concentrations were found in the alpine soils at the top of the hillslope. Soil carbon stock, soil solution dissolved organic carbon (DOC) and factors representing site hydrology were the best predictors of NO(3)(-) concentration, with highest concentrations at low productivity sites with low DOC and freely-draining soils. These factors act as proxies for changing net biological uptake and soil/water contact time, and therefore support the hypothesis that spatial variations in soil solution NO(3)(-) are controlled by habitat N retention capacity. Soil percent carbon was a better predictor of soil solution inorganic N concentration than mass of soil carbon. NH(4)(+) was less affected by soil hydrology than NO(3)(-) and showed the effects of net mineralization inputs, particularly at Racomitrium heath and peaty sites. Soil solution dissolved organic N concentration was strongly related to both DOC and temperature, with a stronger temperature effect at more productive sites. Due to the spatial heterogeneity in N leaching potential, a fine-scale approach to assessing surface water vulnerability to N leaching is recommended over the broad scale, critical loads approach currently in use, particularly for sensitive areas. Copyright © 2012 Elsevier B.V. All rights reserved.

[Computational chemistry in structure-based drug design].

PubMed

Cao, Ran; Li, Wei; Sun, Han-Zi; Zhou, Yu; Huang, Niu

2013-07-01

Today, the understanding of the sequence and structure of biologically relevant targets is growing rapidly and researchers from many disciplines, physics and computational science in particular, are making significant contributions to modern biology and drug discovery. However, it remains challenging to rationally design small molecular ligands with desired biological characteristics based on the structural information of the drug targets, which demands more accurate calculation of ligand binding free-energy. With the rapid advances in computer power and extensive efforts in algorithm development, physics-based computational chemistry approaches have played more important roles in structure-based drug design. Here we reviewed the newly developed computational chemistry methods in structure-based drug design as well as the elegant applications, including binding-site druggability assessment, large scale virtual screening of chemical database, and lead compound optimization. Importantly, here we address the current bottlenecks and propose practical solutions.

Ablation, Thermal Response, and Chemistry Program for Analysis of Thermal Protection Systems

NASA Technical Reports Server (NTRS)

Milos, Frank S.; Chen, Yih-Kanq

2010-01-01

In previous work, the authors documented the Multicomponent Ablation Thermochemistry (MAT) and Fully Implicit Ablation and Thermal response (FIAT) programs. In this work, key features from MAT and FIAT were combined to create the new Fully Implicit Ablation, Thermal response, and Chemistry (FIATC) program. FIATC is fully compatible with FIAT (version 2.5) but has expanded capabilities to compute the multispecies surface chemistry and ablation rate as part of the surface energy balance. This new methodology eliminates B' tables, provides blown species fractions as a function of time, and enables calculations that would otherwise be impractical (e.g. 4+ dimensional tables) such as pyrolysis and ablation with kinetic rates or unequal diffusion coefficients. Equations and solution procedures are presented, then representative calculations of equilibrium and finite-rate ablation in flight and ground-test environments are discussed.

Synthesis and characterization of polyethylene glycol mediated silver nanoparticles by the green method.

PubMed

Shameli, Kamyar; Ahmad, Mansor Bin; Jazayeri, Seyed Davoud; Sedaghat, Sajjad; Shabanzadeh, Parvaneh; Jahangirian, Hossein; Mahdavi, Mahnaz; Abdollahi, Yadollah

2012-01-01

The roles of green chemistry in nanotechnology and nanoscience fields are very significant in the synthesis of diverse nanomaterials. Herein, we report a green chemistry method for synthesized colloidal silver nanoparticles (Ag NPs) in polymeric media. The colloidal Ag NPs were synthesized in an aqueous solution using silver nitrate, polyethylene glycol (PEG), and β-D-glucose as a silver precursor, stabilizer, and reducing agent, respectively. The properties of synthesized colloidal Ag NPs were studied at different reaction times. The ultraviolet-visible spectra were in excellent agreement with the obtained nanostructure studies performed by transmission electron microscopy (TEM) and their size distributions. The Ag NPs were characterized by utilizing X-ray diffraction (XRD), zeta potential measurements and Fourier transform infrared (FT-IR). The use of green chemistry reagents, such as glucose, provides green and economic features to this work.

Micromotors for "Chemistry-on-the-Fly".

PubMed

Karshalev, Emil; Esteban-Fernández de Ávila, Berta; Wang, Joseph

2018-03-21

This perspective reviews mobile micro/nanomotor scaffolds for performing "chemistry-on-the-fly". Synthetic nano/micromotors offer great versatility and distinct advantages in diverse chemical applications owing to their efficient propulsion and facile surface functionalization that allow these mobile platforms to move and disperse reactive materials across the solution. Such dynamic microreactors have led to accelerated chemical processes, including organic pollutant degradation, metal chelation, biorecognition, redox chemistry, chemical "writing", and a variety of other chemical transformations. Representative examples of such micromotor-enhanced chemical reactions are discussed, focusing on the specific chemical role of these mobile microreactors. The advantages, gaps and limitations of using micromotors as mobile chemical platforms are discussed, concluding with the future prospects of this emerging field. We envision that artificial nano/micromotors will become attractive dynamic tools for speeding up and enhancing "on-the-fly" chemical reactions.

Shape control VO2 nanorods prepared by soft chemistry and electrochemical method

NASA Astrophysics Data System (ADS)

Simo, A.; Sibanyoni, J.; Fuku, X.; Numan, N.; Omorogbe, S.; Maaza, M.

2018-07-01

"Bottom up" approach is of primary interest for chemistry and materials science because the fundamental building blocks are atoms. Thus colloidal chemical synthetic methods can be utilized to prepare uniform nanocrystals with controlled particle size. In the following work of study, thermochromic VO2 nanostructures were prepared by hydrothermal technique soft chemistry. We concentrate on solution phase synthetic methods that enable a proper shape and size control of metal oxide nanocrystals. Their structural properties were studied by Scanning Electron Microscopy (SEM), Fourier Transform IR (FTIR) and Differential Scanning Calorimetry (DSC). It is demonstrated that the surfactant assistance (NaOH) has great influence on the morphology-control of the material. Electrochemical properties of the nanospheres show good stability after 20 cycles and the surface diffusion coefficient was calculated to be 5 × 10-6 cm2 s-1.

Controls on soil solution nitrogen along an altitudinal gradient in the Scottish uplands

NASA Astrophysics Data System (ADS)

Jackson-Blake, L.; Helliwell, R. C.; Britton, A. J.; Gibbs, S.; Coull, M. C.; Dawson, L.

2012-04-01

Nitrogen (N) deposition continues to threaten upland ecosystems, contributing to acidification, eutrophication and biodiversity loss. We present results from a monitoring study aimed at investigating the fate of this deposited N within a relatively pristine catchment in the Cairngorm Mountains (Scotland). Six sites were established along an elevation gradient (486 - 908 m) spanning the key habitats of temperate maritime uplands. Bulk deposition chemistry, soil carbon content, soil solution chemistry, soil temperature and soil moisture content were monitored over a 5 year period, making this the first study of its kind in a maritime Alpine environment. Results were used to assess spatial variability in soil solution N and to investigate the factors and processes driving this variability. Highest soil solution inorganic N concentrations were found in the alpine soils at the top of the hillslope. Soil carbon stock, dissolved organic carbon concentration and factors representing site hydrology were the best predictors of nitrate concentration. These factors act as proxies for changing net biological uptake and soil/water contact time, and support the hypothesis that spatial variations in soil solution nitrate are controlled by habitat N retention capacity. Soil percent carbon was a better predictor of soil solution N concentration than mass of carbon. Ammonium was less affected by soil hydrology than nitrate and showed the effects of net mineralization inputs, particularly at Racomitrium heath and peaty sites. We hypothesize that high ammonium concentrations at the Racomitrium heath are related to the mineralization of microbial cell tissue during times of stress, largely in the absence of plant uptake. Due to the spatial heterogeneity in N leaching potential, a fine-scale approach to assessing surface water vulnerability to N leaching is recommended over the broad scale, critical loads approach currently in use, particularly for sensitive areas.

A functionalized poly(ethylene glycol)-based bioassay surface chemistry that facilitates bio-immobilization and inhibits non-specific protein, bacterial, and mammalian cell adhesion

PubMed Central

Harbers, Gregory M.; Emoto, Kazunori; Greef, Charles; Metzger, Steven W.; Woodward, Heather N.; Mascali, James J.; Grainger, David W.; Lochhead, Michael J.

2008-01-01

This paper describes a new bioassay surface chemistry that effectively inhibits non-specific biomolecular and cell binding interactions, while providing a capacity for specific immobilization of desired biomolecules. Poly(ethylene glycol) (PEG) as the primary component in nonfouling film chemistry is well-established, but the multicomponent formulation described here is unique in that it (1) is applied in a single, reproducible, solution-based coating step; (2) can be applied to diverse substrate materials without the use of special primers; and (3) is readily functionalized to provide specific attachment chemistries. Surface analysis data are presented, detailing surface roughness, polymer film thickness, and film chemistry. Protein non-specific binding assays demonstrate significant inhibition of serum, fibrinogen, and lysozyme adsorption to coated glass, indium tin oxide, and tissue culture polystyrene dishes. Inhibition of S. aureus and K. pneumoniae microbial adhesion in a microfluidic flow cell, and inhibition of fibroblast cell adhesion from serum-based cell culture is shown. Effective functionalization of the coating is demonstrated by directing fibroblast adhesion to polymer surfaces activated with an RGD peptide. Batch-to-batch reproducibility data are included. The in situ cross-linked PEG-based coating chemistry is unique in its formulation, and its surface properties are attractive for a broad range of in vitro bioassay applications. PMID:18815622

Selecting automation for the clinical chemistry laboratory.

PubMed

Melanson, Stacy E F; Lindeman, Neal I; Jarolim, Petr

2007-07-01

Laboratory automation proposes to improve the quality and efficiency of laboratory operations, and may provide a solution to the quality demands and staff shortages faced by today's clinical laboratories. Several vendors offer automation systems in the United States, with both subtle and obvious differences. Arriving at a decision to automate, and the ensuing evaluation of available products, can be time-consuming and challenging. Although considerable discussion concerning the decision to automate has been published, relatively little attention has been paid to the process of evaluating and selecting automation systems. To outline a process for evaluating and selecting automation systems as a reference for laboratories contemplating laboratory automation. Our Clinical Chemistry Laboratory staff recently evaluated all major laboratory automation systems in the United States, with their respective chemistry and immunochemistry analyzers. Our experience is described and organized according to the selection process, the important considerations in clinical chemistry automation, decisions and implementation, and we give conclusions pertaining to this experience. Including the formation of a committee, workflow analysis, submitting a request for proposal, site visits, and making a final decision, the process of selecting chemistry automation took approximately 14 months. We outline important considerations in automation design, preanalytical processing, analyzer selection, postanalytical storage, and data management. Selecting clinical chemistry laboratory automation is a complex, time-consuming process. Laboratories considering laboratory automation may benefit from the concise overview and narrative and tabular suggestions provided.

Effects of Sex on Intra-Individual Variance in Urinary Solutes in Stone-Formers Collected from a Single Clinical Laboratory

PubMed Central

Perry, Guy M. L.; Scheinman, Steven J.; Asplin, John R.

2013-01-01

Background/Aims Our work in a rodent model of urinary calcium suggests genetic and gender effects on increased residual variability in urine chemistries. Based on these findings, we hypothesized that sex would similarly be associated with residual variation in human urine solutes. Sex-related effects on residuals might affect the establishment of physiological baselines and error in medical assays. Methods We tested the effects of sex on residual variation in urine chemistry by estimating coefficients of variation (CV) for urinary solutes in paired sequential 24-h urines (≤72 hour interval) in 6,758 females and 9,024 males aged 16–80 submitted to a clinical laboratory. Results Females had higher CVs than males for urinary phosphorus overall at the False Discovery Rate (P<0.01). There was no effect of sex on CV for calcium (P>0.3). Males had higher CVs for citrate (P<0.01) from ages 16–45 and females higher CVs for citrate (P<0.01) from ages 56–80, suggesting effects of an extant oestral cycle on residual variance. Conclusions Our findings indicate the effects of sex on residual variance of the excretion of urinary solutes including phosphorus and citrate; differences in CV by sex might reflect dietary lability, differences in the fidelity of reporting or genetic differentiation in renal solute consistency. Such an effect could complicate medical analysis by the addition of random error to phenotypic assays. Renal analysis might require explicit incorporation of heterogeneity among factorial effects, and for sex in particular. PMID:23840293

Individual and Co Transport Study of Titanium Dioxide NPs and Zinc Oxide NPs in Porous Media

PubMed Central

Kumari, Jyoti; Mathur, Ankita; Rajeshwari, A.; Venkatesan, Arthi; S, Satyavati; Pulimi, Mrudula; Chandrasekaran, Natarajan; Nagarajan, R.; Mukherjee, Amitava

2015-01-01

The impact of pH and ionic strength on the mobility (individual and co-transport) and deposition kinetics of TiO2 and ZnO NPs in porous media was systematically investigated in this study. Packed column experiments were performed over a series of environmentally relevant ionic strengths with both NaCl (0.1−10 mM) and CaCl2 (0.01–0.1mM) solutions and at pH 5, 7, and 9. The transport of TiO2 NPs at pH 5 was not significantly affected by ZnO NPs in solution. At pH 7, a decrease in TiO2 NP transport was noted with co-existence of ZnO NPs, while at pH 9 an increase in the transport was observed. At pH 5 and 7, the transport of ZnO NPs was decreased when TiO2 NPs was present in the solution, and at pH 9, an increase was noted. The breakthrough curves (BTC) were noted to be sensitive to the solution chemistries; the decrease in the breakthrough plateau with increasing ionic strength was observed under all examined pH (5, 7, and 9). The retention profiles were the inverse of the plateaus of BTCs, as expected from mass balance considerations. Overall, the results from this study suggest that solution chemistries (ionic strength and pH) are likely the key factors that govern the individual and co-transport behavior of TiO2 and ZnO NPs in sand. PMID:26252479

A study of hydrogen peroxide chemistry and photochemistry in tea stain solution with relevance to clinical tooth whitening.

PubMed

Young, Nigel; Fairley, Peter; Mohan, Veena; Jumeaux, Coline

2012-12-01

Tooth whitening using hydrogen peroxide is a complex process, and there is still some controversy about the roles of pH, temperature, chemical activators, and the use of light irradiation. In this work the basic interactions between whitening agents and stain molecules are studied in simple solutions, thus avoiding the physics of diffusion and light penetration in the tooth to give clarity on the basic chemistry which is occurring. The absorbance of tea stain solution at 450 nm was measured over a period of 40 min, with various compositions of whitening agent added (including hydrogen peroxide, ferrous gluconate and potassium hydroxide) and at the same time the samples were subjected to blue light (465 nm) or infra-red light (850 nm) irradiation, or alternatively they were heated to 37°C. It is shown that the reaction rates between chromogens in the tea solution and hydrogen peroxide can be accelerated significantly using ferrous gluconate activator and blue light irradiation. Infra red irradiation does not increase the reaction rate through photochemistry, it serves only to increase the temperature. Raising the temperature leads to inefficiency through the acceleration of exothermic decomposition reactions which produce only water and oxygen. By carrying out work in simple solution it was possible to show that ferrous activators and blue light irradiation significantly enhance the whitening process, whereas infra red irradiation has no significant effect over heating. The importance of controlling the pH within the tooth structure during whitening is also demonstrated. Copyright © 2012 Elsevier Ltd. All rights reserved.

On Teaching Thermodynamics

ERIC Educational Resources Information Center

Debbasch, F.

2011-01-01

The logical structure of classical thermodynamics is presented in a modern, geometrical manner. The first and second law receive clear, operatively oriented statements and the Gibbs free energy extremum principle is fully discussed. Applications relevant to chemistry, such as phase transitions, dilute solutions theory and, in particular, the law…

Exam Question Exchange.

ERIC Educational Resources Information Center

Alexander, John J., Ed.

1987-01-01

Contains two articles relating to chemistry examination questions. One provides examples of how to sequence multiple choice questions so that partial credit may be given for some responses. The second includes a question and solution dealing with stereoisomerism as a result of free radical chlorination of a nonstereoisometic substance. (TW)

Computer Series, 83. Bits and Pieces, 34.

ERIC Educational Resources Information Center

Moore, John W., Ed.

1987-01-01

Contains seven articles about computer applications to chemistry instruction. Includes descriptions of a three-dimensional animation of a potential energy surface, numerical solutions of kinetic equations, applications for spectroscopy courses, a computer-controlled experiment on the tin/lead solid/liquid phase diagram, an inexpensive thermistor…

Measurement of Solution Viscosity via Diffusion-Ordered NMR Spectroscopy (DOSY)

ERIC Educational Resources Information Center

Li, Weibin; Kagan, Gerald; Hopson, Russell; Williard, Paul G.

2011-01-01

Increasingly, the undergraduate chemistry curriculum includes nuclear magnetic resonance (NMR) spectroscopy. Advanced NMR techniques are often taught including two-dimensional gradient-based experiments. An investigation of intermolecular forces including viscosity, by a variety of methods, is often integrated in the undergraduate physical and…

Single-Walled Carbon Nanotubes Induce Pulmonary and Vascular Response Following Intratracheal Instillation

EPA Science Inventory

Carbon-based nanotubes have been shown to induce varying degrees of pulmonary response in rodents influenced by the dose, the extent of agglomeration, the chemistry of the suspension solution, and the functional properties. We hypothesized that low concentrations of non-modified ...

Baking Soda Science.

ERIC Educational Resources Information Center

Science Activities, 1994

1994-01-01

Discusses the basic principles of baking soda chemistry including the chemical composition of baking soda, its acid-base properties, the reaction of bicarbonate solution with calcium ions, and a description of some general types of chemical reactions. Includes a science activity that involves removing calcium ions from water. (LZ)

SONOCHEMICAL DECHLORINATION OF HAZARDOUS WASTES IN AQUEOUS SYSTEMS. (R825513C004)

EPA Science Inventory

Physical processes resulting from ultrasonication of aqueous solutions and suspensions produce extreme conditions that can affect the chemistry of dissolved and suspended chemicals. The purpose of this work was to explore the use of sonochemistry in treating chlorinated chemic...

Development of 6.1 A Materials for IR Applications

DTIC Science & Technology

2011-12-01

growth and electrical characterization. Additionally, we would like to thank Dr. Sudhir Trivedi of Brimrose Corporation for his assistance with etchant...ARL from Brimrose Corp with extensive 7 knowledge of chemistry related to materials science, we have come across a promising solution that reveals

NEW ADVANCES IN BORON SOIL CHEMISTRY

EPA Science Inventory

Boron is an essential plant micronutrient for which the range between deficiency and toxicity is narrower than for any other nutrient element. Plants respond directly to the amount of B in soil solution and only indirectly to the amount of B adsorbed on soil particle surfaces. ...

NEW ADVANCES IN BORON SOIL CHEMISTRY - Paper

EPA Science Inventory

Boron is an essential plant micronutrient for which the range between deficiency and toxicity is narrower than for any other nutrient element. Plants respond directly to the amount of B in soil solution and only indirectly to the amount of B adsorbed on soil particle surfaces. ...

Quasiperiodicity and chaos in post-AGB stars

NASA Astrophysics Data System (ADS)

Icke, V.

2003-03-01

This is a mini-presentation of three subjects, which are all related to the atmospheric motion in post-AGB stars. First, a summary of my 1990 equation of a driven stellar oscillator that exhibits chaotic solutions. Second, an advertisement for the subtle interplay of hydrodynamics, gas/dust drift, gas chemistry, dust formation, and radiation pressure, as presented in the thesis by Simis. Third, a new model equation for nonspherical stellar oscillations that resembles the FPU-equation which shows permanent non-equilibrium, with possibly intermittent solutions.

Test and Evaluation of a Pilot System for Ion Exchange Treatment of Cadmium Cyanide Wastes

DTIC Science & Technology

1993-09-01

rate, metal concentration and solution chemistry , and temperature. These factors affect the diffusion rate of metal ions from the bulk solution to the...Changes in Cd2+ or CN- resin capacity and removal efficiency after a number of regeneration cycles; • Discharge leakage levels of Cd2+ and CN- after...a filter to remove any suspended solids, an activated-carbon column to remove any organic matter (this step was not utilized since organic levels

Solution chemistry effects on orthophosphate adsorption by cationized solid wood residues

Treesearch

K.G. Karthikeyan; Mandla A. Tshabalala; D. Wang; M. Kalbasi

2004-01-01

Adsorption of orthophosphate anions in aqueous solution by cationized milled solid wood residues was characterized as a function of sorbate-to- sorbent ratio (=0.001-2.58 mmol of P/g substrate), pH (3-9), ionic strength, I (no I control; 0.001 and 0.01 M NaCl), reaction time (4 min to 24 h), and in the presence of other competing anions (0.08-50 mM SO4 2-; 0.08-250 mM...

Structure, Bonding and Surface Chemistry of Metal Oxide Nanoclusters

DTIC Science & Technology

2015-06-23

studies to cobalt and chromium oxides and to both oxides and pure metal clusters of aluminum, using acetonitrile as the ligand. The chromium solutions...seen in molecular beam experiments. The cobalt oxide sample produced a blue solution, and mass spectra had a single main peak at 551 amu. Mass...of cobalt and nickel oxide cluster cations," J. Phys. Chem. A 116, 5398-5404 (2012). DOI: 10.1021/jp302560p. 4. A. M. Ricks, A. D. Brathwaite, M

MOLECULAR THEORY OF HYDROPHOBIC EFFECTS: "She is too mean to have her name repeated."*

NASA Astrophysics Data System (ADS)

Pratt, Lawrence R.

2002-10-01

This paper reviews the molecular theory of hydrophobic effects relevant to biomolecular structure and assembly in aqueous solution. Recent progress has resulted in simple, validated molecular statistical thermodynamic theories and clarification of confusing theories of decades ago. Current work is resolving effects of wider variations of thermodynamic state, e.g., pressure denaturation of soluble proteins, and more exotic questions such as effects of surface chemistry in treating stability of macromolecular structures in aqueous solution.

Building Units Design and Scale Chemistry

NASA Astrophysics Data System (ADS)

Férey, Gérard

2000-06-01

The concept of a building unit (BU) is used in two ways: the first is an a posteriori tool for description of structures which can be used to imagine new topologies originating from the description; the second one, restricted to the routes leading to the solid from the solution, starts from the reality of these building units in the solution to design new solids obtained by the tuned precipitation of these BUs with proper counterions. The room temperature and the hydrothermal routes are examined. The existence of BUs with different sizes with close topologies, revealed by numerous examples, leads us to define the notion of "scale chemistry" which concerns the edification of solids with various BUs, either organic, hybrid, or inorganic, and the consequences it has for the corresponding frameworks and the voids they generate. Not only the framework is important, and applications of the existence of large cavities are discussed. The paper ends with a discussion of the new trends which arise from this topological concept.

Comparison of free radicals formation induced by cold atmospheric plasma, ultrasound, and ionizing radiation.

PubMed

Rehman, Mati Ur; Jawaid, Paras; Uchiyama, Hidefumi; Kondo, Takashi

2016-09-01

Plasma medicine is increasingly recognized interdisciplinary field combining engineering, physics, biochemistry and life sciences. Plasma is classified into two categories based on the temperature applied, namely "thermal" and "non-thermal" (i.e., cold atmospheric plasma). Non-thermal or cold atmospheric plasma (CAP) is produced by applying high voltage electric field at low pressures and power. The chemical effects of cold atmospheric plasma in aqueous solution are attributed to high voltage discharge and gas flow, which is transported rapidly on the liquid surface. The argon-cold atmospheric plasma (Ar-CAP) induces efficient reactive oxygen species (ROS) in aqueous solutions without thermal decomposition. Their formation has been confirmed by electron paramagnetic resonance (EPR) spin trapping, which is reviewed here. The similarities and differences between the plasma chemistry, sonochemistry, and radiation chemistry are explained. Further, the evidence for free radical formation in the liquid phase and their role in the biological effects induced by cold atmospheric plasma, ultrasound and ionizing radiation are discussed. Copyright © 2016 Elsevier Inc. All rights reserved.

Self-assembled monolayer and method of making

DOEpatents

Fryxell, Glen E [Kennewick, WA; Zemanian, Thomas S [Richland, WA; Liu, Jun [West Richland, WA; Shin, Yongsoon [Richland, WA

2003-03-11

According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.

Self-assembled monolayer and method of making

DOEpatents

Fryxell, Glen E.; Zemanian, Thomas S.; Liu, Jun; Shin, Yongsoon

2004-05-11

According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.

Self-Assembled Monolayer And Method Of Making

DOEpatents

Fryxell, Glen E.; Zemanian, Thomas S.; Liu, Jun; Shin, Yongsoon

2004-06-22

According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.

Self-Assembled Monolayer And Method Of Making

DOEpatents

Fryxell, Glen E.; Zemanian, Thomas S.; Liu, Jun; Shin, Yongsoon

2005-01-25

According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.

Investigation of on-line chelant addition to PWR steam generators. Annual report, 1981

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tvedt, T.J.; Wallace, S.L.; Griffin, F. Jr.

1982-11-01

The thermostability of both ethylenediaminetetraacetic acid (EDTA) and hydroxyethylethylenediamininetriacetic acid (HEDTA) metal chelates in all volatile treatment water chemistry (AVT) was shown to be greater than or equal to thermostability of EDTA metal chelates in phosphate-sulfite water chemistry. HEDTA metal chelates were shown to have a much greater stability than EDTA metal chelates. Using samples taken from the EDTA metal chelate thermostability studies and samples from Commonwealth Research Corporation (CRC) model steam generators (MSG), EDTA decomposition products were determined. Active metal surfaces were shown to become passivated when exposed to EDTA and HEDTA concentrations as high as 0.1% w/w inmore » AVT. Trace amounts of iron in the water were found to increase the rate of passivation. Material balance and visual inspection data from CRC model steam generators showed that metal is being transported through and cleaning from the MSG's. EDTA metal chelates were removed from chelate solutions by passing the solutions over strong anion exchange resins.« less

Reactive solute transport in an acidic stream: Experimental pH increase and simulation of controls on pH, aluminum, and iron

USGS Publications Warehouse

Broshears, R.E.; Runkel, R.L.; Kimball, B.A.; McKnight, Diane M.; Bencala, K.E.

1996-01-01

Solute transport simulations quantitatively constrained hydrologic and geochemical hypotheses about field observations of a pH modification in an acid mine drainage stream. Carbonate chemistry, the formation of solid phases, and buffering interactions with the stream bed were important factors in explaining the behavior of pH, aluminum, and iron. The precipitation of microcrystalline gibbsite accounted for the behavior of aluminum; precipitation of Fe(OH)3 explained the general pattern of iron solubility. The dynamic experiment revealed limitations on assumptions that reactions were controlled only by equilibrium chemistry. Temporal variation in relative rates of photoreduction and oxidation influenced iron behavior. Kinetic limitations on ferrous iron oxidation and hydrous oxide precipitation and the effects of these limitations on field filtration were evident. Kinetic restraints also characterized interaction between the water column and the stream bed, including sorption and desorption of protons from iron oxides at the sediment-water interface and post-injection dissolution of the precipitated aluminum solid phase.

Effects of Solution Chemistry on Nano-Bubbles Transport in Saturated Porous Media

NASA Astrophysics Data System (ADS)

Hamamoto, S.; Takemura, T.; Suzuki, K.; Nihei, N.; Nishimura, T.

2017-12-01

Nano-bubbles (NBs) have a considerable potential for the remediation of soil and groundwater contaminated by organic compounds, especially when used in conjunction with bioremediation technologies. Understanding the transport mechanisms of NBs in soils is essential to optimize NB-based remediation techniques. In this study, one-dimensional column transport experiments using glass beads with 0.1 mm size were conducted, where NBs created by oxygen gas at different pH and ionic strength were injected to the column at the constant flow rate. The NBs concentration in the effluent was quantified using a resonant mass measurement technique. Effects of solution chemistry of the NBs water on NB transport in the porous media were investigated. The results showed that attachment of NBs was enhanced under higher ionic strength and lower pH conditions, caused by the reduced repulsive force between NBs and glass beads. In addition, bubble size distributions in the effluents showed that relatively larger NBs were retained in the column. This trend was more significant at lower pH condition.

Solid-phase synthesis of protein-polymers on reversible immobilization supports.

PubMed

Murata, Hironobu; Carmali, Sheiliza; Baker, Stefanie L; Matyjaszewski, Krzysztof; Russell, Alan J

2018-02-27

Facile automated biomacromolecule synthesis is at the heart of blending synthetic and biologic worlds. Full access to abiotic/biotic synthetic diversity first occurred when chemistry was developed to grow nucleic acids and peptides from reversibly immobilized precursors. Protein-polymer conjugates, however, have always been synthesized in solution in multi-step, multi-day processes that couple innovative chemistry with challenging purification. Here we report the generation of protein-polymer hybrids synthesized by protein-ATRP on reversible immobilization supports (PARIS). We utilized modified agarose beads to covalently and reversibly couple to proteins in amino-specific reactions. We then modified reversibly immobilized proteins with protein-reactive ATRP initiators and, after ATRP, we released and analyzed the protein polymers. The activity and stability of PARIS-synthesized and solution-synthesized conjugates demonstrated that PARIS was an effective, rapid, and simple method to generate protein-polymer conjugates. Automation of PARIS significantly reduced synthesis/purification timelines, thereby opening a path to changing how to generate protein-polymer conjugates.

Silica metal-oxide vesicles catalyze comprehensive prebiotic chemistry.

PubMed

Bizzarri, Bruno Mattia; Botta, Lorenzo; Pérez-Valverde, Maritza Iveth; Saladino, Raffaele; Di Mauro, Ernesto; Garcia Ruiz, Juan Manuel

2018-03-30

It has recently been demonstrated that mineral self-assembled structures catalyzing prebiotic chemical reactions may form in natural waters derived from serpentinization, a geological process widespread in the early stages of Earth-like planets. We have synthesized self-assembled membranes by mixing microdrops of metal solutions with alkaline silicate solutions in the presence of formamide (NH2CHO), a single carbon molecule, at 80ºC. We found that these bilayer membranes, made of amorphous silica and metal oxide-hydroxide nanocrystals, catalyze the condensation of formamide, yielding the four nucleobases of RNA, three aminoacids and several carboxylic acids in a single pot experiment. Besides manganese, iron and magnesium, two abundant elements in the earliest Earth crust that are key in serpentinization reactions, are enough to produce all these biochemical compounds. These results suggest that the transition from inorganic geochemistry to prebiotic organic chemistry is common on a universal scale and, most probably, earlier than ever thought for our planet. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Impact of water chemistry on surface charge and aggregation of polystyrene microspheres suspensions.

PubMed

Lu, Songhua; Zhu, Kairuo; Song, Wencheng; Song, Gang; Chen, Diyun; Hayat, Tasawar; Alharbi, Njud S; Chen, Changlun; Sun, Yubing

2018-07-15

The discharge of microplastics into aquatic environment poses the potential threat to the hydrocoles and human health. The fate and transport of microplastics in aqueous solutions are significantly influenced by water chemistry. In this study, the effect of water chemistry (i.e., pH, foreign salts and humic acid) on the surface charge and aggregation of polystyrene microsphere in aqueous solutions was conducted by batch, zeta potentials, hydrodynamic diameters, FT-IR and XPS analysis. Compared to Na + and K + , the lower negative zeta potentials and larger hydrodynamic diameters of polystyrene microspheres after introduction of Mg 2+ were observed within a wide range of pH (2.0-11.0) and ionic strength (IS, 0.01-500mmol/L). No effect of Cl - , HCO 3 - and SO 4 2- on the zeta potentials and hydrodynamic diameters of polystyrene microspheres was observed at low IS concentrations (<5mmol/L), whereas the zeta potentials and hydrodynamic diameters of polystyrene microspheres after addition of SO 4 2- were higher than that of Cl - and HCO 3 - at high IS concentrations (>10mmol/L). The zeta potentials of polystyrene microspheres after HA addition were decreased at pH2.0-11.0, whereas the lower hydrodynamic diameters were observed at pH<4.0. According to FT-IR and XPS analysis, the change in surface properties of polystyrene microspheres after addition of hydrated Mg 2+ and HA was attributed to surface electrostatic and/or steric repulsions. These investigations are crucial for understanding the effect of water chemistry on colloidal stability of microplastics in aquatic environment. Copyright © 2018 Elsevier B.V. All rights reserved.

An abstraction layer for efficient memory management of tabulated chemistry and flamelet solutions

NASA Astrophysics Data System (ADS)

Weise, Steffen; Messig, Danny; Meyer, Bernd; Hasse, Christian

2013-06-01

A large number of methods for simulating reactive flows exist, some of them, for example, directly use detailed chemical kinetics or use precomputed and tabulated flame solutions. Both approaches couple the research fields computational fluid dynamics and chemistry tightly together using either an online or offline approach to solve the chemistry domain. The offline approach usually involves a method of generating databases or so-called Lookup-Tables (LUTs). As these LUTs are extended to not only contain material properties but interactions between chemistry and turbulent flow, the number of parameters and thus dimensions increases. Given a reasonable discretisation, file sizes can increase drastically. The main goal of this work is to provide methods that handle large database files efficiently. A Memory Abstraction Layer (MAL) has been developed that handles requested LUT entries efficiently by splitting the database file into several smaller blocks. It keeps the total memory usage at a minimum using thin allocation methods and compression to minimise filesystem operations. The MAL has been evaluated using three different test cases. The first rather generic one is a sequential reading operation on an LUT to evaluate the runtime behaviour as well as the memory consumption of the MAL. The second test case is a simulation of a non-premixed turbulent flame, the so-called HM1 flame, which is a well-known test case in the turbulent combustion community. The third test case is a simulation of a non-premixed laminar flame as described by McEnally in 1996 and Bennett in 2000. Using the previously developed solver 'flameletFoam' in conjunction with the MAL, memory consumption and the performance penalty introduced were studied. The total memory used while running a parallel simulation was reduced significantly while the CPU time overhead associated with the MAL remained low.

Forebody and base region real gas flow in severe planetary entry by a factored implicit numerical method. II - Equilibrium reactive gas

NASA Technical Reports Server (NTRS)

Davy, W. C.; Green, M. J.; Lombard, C. K.

1981-01-01

The factored-implicit, gas-dynamic algorithm has been adapted to the numerical simulation of equilibrium reactive flows. Changes required in the perfect gas version of the algorithm are developed, and the method of coupling gas-dynamic and chemistry variables is discussed. A flow-field solution that approximates a Jovian entry case was obtained by this method and compared with the same solution obtained by HYVIS, a computer program much used for the study of planetary entry. Comparison of surface pressure distribution and stagnation line shock-layer profiles indicates that the two solutions agree well.

Nanoporous membranes with electrochemically switchable, chemically stabilized ionic selectivity

NASA Astrophysics Data System (ADS)

Small, Leo J.; Wheeler, David R.; Spoerke, Erik D.

2015-10-01

Nanopore size, shape, and surface charge all play important roles in regulating ionic transport through nanoporous membranes. The ability to control these parameters in situ provides a means to create ion transport systems tunable in real time. Here, we present a new strategy to address this challenge, utilizing three unique electrochemically switchable chemistries to manipulate the terminal functional group and control the resulting surface charge throughout ensembles of gold plated nanopores in ion-tracked polycarbonate membranes 3 cm2 in area. We demonstrate the diazonium mediated surface functionalization with (1) nitrophenyl chemistry, (2) quinone chemistry, and (3) previously unreported trimethyl lock chemistry. Unlike other works, these chemistries are chemically stabilized, eliminating the need for a continuously applied gate voltage to maintain a given state and retain ionic selectivity. The effect of surface functionalization and nanopore geometry on selective ion transport through these functionalized membranes is characterized in aqueous solutions of sodium chloride at pH = 5.7. The nitrophenyl surface allows for ionic selectivity to be irreversibly switched in situ from cation-selective to anion-selective upon reduction to an aminophenyl surface. The quinone-terminated surface enables reversible changes between no ionic selectivity and a slight cationic selectivity. Alternatively, the trimethyl lock allows ionic selectivity to be reversibly switched by up to a factor of 8, approaching ideal selectivity, as a carboxylic acid group is electrochemically revealed or hidden. By varying the pore shape from cylindrical to conical, it is demonstrated that a controllable directionality can be imparted to the ionic selectivity. Combining control of nanopore geometry with stable, switchable chemistries facilitates superior control of molecular transport across the membrane, enabling tunable ion transport systems.Nanopore size, shape, and surface charge all play important roles in regulating ionic transport through nanoporous membranes. The ability to control these parameters in situ provides a means to create ion transport systems tunable in real time. Here, we present a new strategy to address this challenge, utilizing three unique electrochemically switchable chemistries to manipulate the terminal functional group and control the resulting surface charge throughout ensembles of gold plated nanopores in ion-tracked polycarbonate membranes 3 cm2 in area. We demonstrate the diazonium mediated surface functionalization with (1) nitrophenyl chemistry, (2) quinone chemistry, and (3) previously unreported trimethyl lock chemistry. Unlike other works, these chemistries are chemically stabilized, eliminating the need for a continuously applied gate voltage to maintain a given state and retain ionic selectivity. The effect of surface functionalization and nanopore geometry on selective ion transport through these functionalized membranes is characterized in aqueous solutions of sodium chloride at pH = 5.7. The nitrophenyl surface allows for ionic selectivity to be irreversibly switched in situ from cation-selective to anion-selective upon reduction to an aminophenyl surface. The quinone-terminated surface enables reversible changes between no ionic selectivity and a slight cationic selectivity. Alternatively, the trimethyl lock allows ionic selectivity to be reversibly switched by up to a factor of 8, approaching ideal selectivity, as a carboxylic acid group is electrochemically revealed or hidden. By varying the pore shape from cylindrical to conical, it is demonstrated that a controllable directionality can be imparted to the ionic selectivity. Combining control of nanopore geometry with stable, switchable chemistries facilitates superior control of molecular transport across the membrane, enabling tunable ion transport systems. Electronic supplementary information (ESI) available: Experimental procedures, synthesis, and characterization of molecules 1, 2 and 3. Explanation of the electrochemical method for approximating nanopore diameter. Additional XPS spectra. See DOI: 10.1039/C5NR02939B

The first sustainable material designed for air particulate matter capture: An introduction to Azure Chemistry.

PubMed

Zanoletti, A; Bilo, F; Depero, L E; Zappa, D; Bontempi, E

2018-07-15

This work presents a new porous material (SUNSPACE) designed for air particulate matter (PM) capture. It was developed in answer to the European Commission request of an innovative, affordable, and sustainable solution, based on design-driven material, to reduce the concentration of air particulate matter in urban areas. SUNSPACE material was developed from by-products and low-cost materials, such as silica fume and sodium alginate. Its capability to catch ultrafine PM was evaluated by different ad-hoc tests, considering diesel exhaust fumes and incense smoke PM. Despite the fact that procedures and materials can be designed for remediation, the high impact on the environment, for example in terms of natural resources consumption and emissions, are not usually considered. Instead, we believe that the technologies must be always evaluated in terms of material embodied energy (EE) and carbon footprint (CF). We define our approach to solve environment problems by a sustainable methodology "Azure Chemistry". For the SUNSPACE synthesis, the multi-criteria decision analysis was performed to select the best sustainable solution. The emissions and the energies involved in the synthesis of SUNSPACE material were evaluated with the Azure Chemistry approach, showing that this could be the best available technology to face the problem of capturing the PM in urban area. Copyright © 2018 Elsevier Ltd. All rights reserved.

Ethers on Si(001): A Prime Example for the Common Ground between Surface Science and Molecular Organic Chemistry.

PubMed

Pecher, Lisa; Laref, Slimane; Raupach, Marc; Tonner, Ralf

2017-11-20

By using computational chemistry it has been shown that the adsorption of ether molecules on Si(001) under ultrahigh vacuum conditions can be understood with classical concepts of organic chemistry. Detailed analysis of the two-step reaction mechanism-1) formation of a dative bond between the ether oxygen atom and a Lewis acidic surface atom and 2) nucleophilic attack of a nearby Lewis basic surface atom-shows that it mirrors acid-catalyzed ether cleavage in solution. The O-Si dative bond is the strongest of its kind, and the reactivity in step 2 defies the Bell-Evans-Polanyi principle. Electron rearrangement during C-O bond cleavage has been visualized with a newly developed method for analyzing bonding, which shows that the mechanism of nucleophilic substitutions on semiconductor surfaces is identical to molecular S N 2 reactions. Our findings illustrate how surface science and molecular chemistry can mutually benefit from each other and unexpected insight can be gained. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Persistence of Hydrologic Variables and Reactive Stream Solute Concentrations in an East Tennessee Watershed

DOE Office of Scientific and Technical Information (OSTI.GOV)

Koirala, Shesh R; Gentry, Randall W; Mulholland, Patrick J

2011-01-01

Time and frequency domain analyses were conducted on weekly time series of water chemistry (nitrate, sulfate and calcium concentrations) collected from November 1995 to December 2005 at the West Fork of Walker Branch in Oak Ridge, Tennessee to evaluate the extent of their persistence and the relationship of this persistence to discharge and rainfall. In this study, spectral and wavelet analyses provided a theoretical basis for insights into long-term water chemistry behavior. All water chemistry parameters showed some level of persistence that was influenced by rainfall and/or discharge. Short-term persistence (less than a year) was related to the persistence ofmore » rainfall and discharge, whereas long-term persistence (more than a year) was related to the persistence of discharge. The Walker Branch conceptual hydrology model is augmented by these results that relate characteristic periodicities with flowpaths through different zones: the vadose zone (< 20 week period), saturated zone (20-50 week period) and bedrock zone (> 50 week period) with implications for reactive chemistries within the watershed. (C) 2011 Elsevier B.V. All rights reserved.« less

Batteries at NASA - Today and Beyond

NASA Technical Reports Server (NTRS)

Reid, Concha M.

2015-01-01

NASA uses batteries for virtually all of its space missions. Batteries can be bulky and heavy, and some chemistries are more prone to safety issues than others. To meet NASA's needs for safe, lightweight, compact and reliable batteries, scientists and engineers at NASA develop advanced battery technologies that are suitable for space applications and that can satisfy these multiple objectives. Many times, these objectives compete with one another, as the demand for more and more energy in smaller packages dictates that we use higher energy chemistries that are also more energetic by nature. NASA partners with companies and universities, like Xavier University of Louisiana, to pool our collective knowledge and discover innovative technical solutions to these challenges. This talk will discuss a little about NASA's use of batteries and why NASA seeks more advanced chemistries. A short primer on battery chemistries and their chemical reactions is included. Finally, the talk will touch on how the work under the Solid High Energy Lithium Battery (SHELiB) grant to develop solid lithium-ion conducting electrolytes and solid-state batteries can contribute to NASA's mission.

Effect of Hydrofluoric Acid Etching Time on Titanium Topography, Chemistry, Wettability, and Cell Adhesion

PubMed Central

Zahran, R.; Rosales Leal, J. I.; Rodríguez Valverde, M. A.; Cabrerizo Vílchez, M. A.

2016-01-01

Titanium implant surface etching has proven an effective method to enhance cell attachment. Despite the frequent use of hydrofluoric (HF) acid, many questions remain unresolved, including the optimal etching time and its effect on surface and biological properties. The objective of this study was to investigate the effect of HF acid etching time on Ti topography, surface chemistry, wettability, and cell adhesion. These data are useful to design improved acid treatment and obtain an improved cell response. The surface topography, chemistry, dynamic wetting, and cell adhesiveness of polished Ti surfaces were evaluated after treatment with HF acid solution for 0, 2; 3, 5, 7, or 10 min, revealing a time-dependent effect of HF acid on their topography, chemistry, and wetting. Roughness and wetting increased with longer etching time except at 10 min, when roughness increased but wetness decreased. Skewness became negative after etching and kurtosis tended to 3 with longer etching time. Highest cell adhesion was achieved after 5–7 min of etching time. Wetting and cell adhesion were reduced on the highly rough surfaces obtained after 10-min etching time. PMID:27824875

Chemistry in CESM-SE: Evaluation, Performance and Optimization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lamarque, Jean-Francois; Conley, Andrew; Vitt, Francis

2016-01-06

The purpose of the proposed work focused on development of chemistry representation within the Spectral Element (SE) dynamical core as implemented in the Community Earth System Model (CESM). More specifically, a main focus was on the ability of SE to accurately represent tracer transport. The proposed approach was to incrementally increase the complexity of the problem, starting from specified two-dimensional flow and tracers to simulations using specified dynamics and full chemistry. As demonstrated below, we have successfully studied all aspects of the proposed work, although only part of the work has been published in the refereed literature so far. Furthermore,more » because the SE dynamical core has been found to have several deficiencies that are still being investigated for solution, not all proposed tasks were finalized. In addition to the tests for SE performance, in an effort to decrease the computational burden of interactive chemistry, especially in the case of a large number of chemical species and chemical reactions, development on a faster chemical solver and implementation on GPUs has been implemented in CESM under the leadership of John Drake (U. Tennessee).« less

Single-Molecule Reaction Chemistry in Patterned Nanowells

PubMed Central

2016-01-01

A new approach to synthetic chemistry is performed in ultraminiaturized, nanofabricated reaction chambers. Using lithographically defined nanowells, we achieve single-point covalent chemistry on hundreds of individual carbon nanotube transistors, providing robust statistics and unprecedented spatial resolution in adduct position. Each device acts as a sensor to detect, in real-time and through quantized changes in conductance, single-point functionalization of the nanotube as well as consecutive chemical reactions, molecular interactions, and molecular conformational changes occurring on the resulting single-molecule probe. In particular, we use a set of sequential bioconjugation reactions to tether a single-strand of DNA to the device and record its repeated, reversible folding into a G-quadruplex structure. The stable covalent tether allows us to measure the same molecule in different solutions, revealing the characteristic increased stability of the G-quadruplex structure in the presence of potassium ions (K+) versus sodium ions (Na+). Nanowell-confined reaction chemistry on carbon nanotube devices offers a versatile method to isolate and monitor individual molecules during successive chemical reactions over an extended period of time. PMID:27270004

Quantum chemistry simulation on quantum computers: theories and experiments.

PubMed

Lu, Dawei; Xu, Boruo; Xu, Nanyang; Li, Zhaokai; Chen, Hongwei; Peng, Xinhua; Xu, Ruixue; Du, Jiangfeng

2012-07-14

It has been claimed that quantum computers can mimic quantum systems efficiently in the polynomial scale. Traditionally, those simulations are carried out numerically on classical computers, which are inevitably confronted with the exponential growth of required resources, with the increasing size of quantum systems. Quantum computers avoid this problem, and thus provide a possible solution for large quantum systems. In this paper, we first discuss the ideas of quantum simulation, the background of quantum simulators, their categories, and the development in both theories and experiments. We then present a brief introduction to quantum chemistry evaluated via classical computers followed by typical procedures of quantum simulation towards quantum chemistry. Reviewed are not only theoretical proposals but also proof-of-principle experimental implementations, via a small quantum computer, which include the evaluation of the static molecular eigenenergy and the simulation of chemical reaction dynamics. Although the experimental development is still behind the theory, we give prospects and suggestions for future experiments. We anticipate that in the near future quantum simulation will become a powerful tool for quantum chemistry over classical computations.

Kraft lignin chain extension chemistry via propargylation, oxidative coupling, and Claisen rearrangement.

PubMed

Sen, Sanghamitra; Sadeghifar, Hasan; Argyropoulos, Dimitris S

2013-10-14

Despite its aromatic and polymeric nature, the heterogeneous, stochastic, and reactive characteristics of softwood kraft lignin seriously limit its potential for thermoplastic applications. Our continuing efforts toward creating thermoplastic lignin polymers are now focused at exploring propargylation derivatization chemistry and its potential as a versatile novel route for the eventual utilization of technical lignins with a significant amount of molecular control. To do this, we initially report the systematic propargylation of softwood kraft lignin. The synthesized derivatives were extensively characterized with thermal methods (DSC, TGA), (1)H, (13)C, and quantitative (31)P NMR and IR spectroscopies. Further on, we explore the versatile nature of the lignin pendant propargyl groups by demonstrating two distinct chain extension chemistries; the solution-based, copper-mediated, oxidative coupling and the thermally induced, solid-state, Claissen rearrangement polymerization chemistries. Overall, we show that it is possible to modulate the reactivity of softwood kraft lignin via a combination of methylation and chain extension providing a rational means for the creation of higher molecular weight polymers with the potential for thermoplastic materials and carbon fibers with the desired control of structure-property relations.

Chemical Calculations; An Audiotutorial Approach.

ERIC Educational Resources Information Center

Lower, Stephen K.

An audiotutorial approach to problem-solving in college chemistry relying upon audio tapes is available. The program is designed to increase the teacher's effectiveness by providing individualized attention to student difficulties related to problem-solving. Problem solutions are recorded on audio tapes (designed for use with Sony TC-160 cassettes…

Density Gradients in Chemistry Teaching

ERIC Educational Resources Information Center

Miller, P. J.

1972-01-01

Outlines experiments in which a density gradient might be used to advantage. A density gradient consists of a column of liquid, the composition and density of which varies along its length. The procedure can be used in analysis of solutions and mixtures and in density measures of solids. (Author/TS)

Raoult's Law: A General Chemistry Experiment.

ERIC Educational Resources Information Center

Steffel, Margaret J.

1983-01-01

To make material on Raoult's law more meaningful, students complete exercises on paper, in the laboratory, and with molecular models. Paper exercises give practice using the law; laboratory work illustrates behavior of real solutions; and models show relationships between properties of individual molecules and of matter in bulk. (JN)

Chemical Principles Revisited: Annotating Reaction Equations.

ERIC Educational Resources Information Center

Tykodi, R. J.

1987-01-01

Urges chemistry teachers to have students annotate the chemical reactions in aqueous-solutions that they see in their textbooks and witness in the laboratory. Suggests this will help students recognize the reaction type more readily. Examples are given for gas formation, precipitate formation, redox interaction, acid-base interaction, and…

TRICHLOROETHYLENE ADSORPTION BY ACTIVATED CARBON PRELOADED WITH HUMIC SUBSTANCES: EFFECTS OF SOLUTION CHEMISTRY. (R828157)

EPA Science Inventory

Abstract

Trichloroethylene (TCE) adsorption by activated carbon previously loaded ("preloaded") with humic substances was found to decrease with increasing concentrations of monovalent ions (NaCl), calcium (until solubility was exceeded), or dissolved oxygen in...

Kinetic Study of Adsorption Processes in Solution: An Undergraduate Physical Chemistry Experiment.

ERIC Educational Resources Information Center

Casado, Julio; And Others

1985-01-01

Background information, apparatus needed, procedures used, and results obtained are provided for a simple kinetic method for the monitoring of adsorption processes. The method, which involved adsorption of crystal violet onto activated carbon, is suitable for classroom and/or research purposes. (JN)

HYDROLOGIC FLOWPATHS INFLUENCE INORGANIC AND ORGANIC NUTRIENT LEACHING IN A FOREST SOIL

EPA Science Inventory

Hydrologic pathways through soil affect element leaching by determining the relative importance of biogeochemical processes such as sorption and decomposition. We used stable hydrogen isotopes of water (δD) to examine the influence of flowpaths on soil solution chemistry in a mat...

Molecular Weight and Molecular Weight Distributions in Synthetic Polymers.

ERIC Educational Resources Information Center

Ward, Thomas Carl

1981-01-01

Focuses on molecular weight and molecular weight distributions (MWD) and models for predicting MWD in a pedagogical way. In addition, instrumental methods used to characterize MWD are reviewed with emphasis on physical chemistry of each, including end-group determination, osmometry, light scattering, solution viscosity, fractionation, and…

Equilibrium and kinetic models for colloid release under transient solution chemistry conditions

USDA-ARS?s Scientific Manuscript database

We present continuum models to describe colloid release in the subsurface during transient physicochemical conditions. Our modeling approach relates the amount of colloid release to changes in the fraction of the solid surface area that contributes to retention. Equilibrium, kinetic, equilibrium and...

Overhead Projector Demonstrations: Some Ideas from the Past.

ERIC Educational Resources Information Center

Kolb, Doris

1987-01-01

Describes nine chemistry demonstrations that can be done using an overhead projector. Includes demonstrations on common ion effect, crystal formation from supersaturated solutions, making iron positive with nitric acid, optical activity, carbon dioxide in human breath, amphoteric hydroxides, the surface tension of mercury, and natural acid-base…

How Students Cope with a Procedureless Lab Exercise.

ERIC Educational Resources Information Center

Pickering, Miles; Crabtree, Robert H.

1979-01-01

Reports a study conducted to determine how students cope with a procedureless laboratory situation in physical chemistry. Students are expected to use ingenuity, determine choice of sample size, conditions, and temperature extrapolation in an experiment on measuring heat of solution of an unknown salt. (Author/SA)

Microscale--The Way of the Future.

ERIC Educational Resources Information Center

Waterman, Edward L.; Thompson, Stephen

1989-01-01

Small-scale chemistry employs a modern design philosophy and small, inexpensive plastic apparatus to create a learning laboratory that fosters creativity, invention, and problem solving. This article describes the characteristics of the small-scale activities. A n-solutions chemical reaction matrix is provided with examples of classroom use. (YP)

Formation of Aqueous Suspensions of Fullerenes

EPA Science Inventory

Colloidal suspensions of C60, C70 and a derivative of C60, PCBM ([6,6]-Phenyl C61-butyric acid methyl ester) were produced by extended mixing in water. We examined the contribution of background solution chemistry (pH, ionic strength) on the formation kinetics of colloidal suspe...

Collaborative routes to clarifying the murky waters of aqueous supramolecular chemistry.

PubMed

Cremer, Paul S; Flood, Amar H; Gibb, Bruce C; Mobley, David L

2017-12-19

On planet Earth, water is everywhere: the majority of the surface is covered with it; it is a key component of all life; its vapour and droplets fill the lower atmosphere; and even rocks contain it and undergo geomorphological changes because of it. A community of physical scientists largely drives studies of the chemistry of water and aqueous solutions, with expertise in biochemistry, spectroscopy and computer modelling. More recently, however, supramolecular chemists - with their expertise in macrocyclic synthesis and measuring supramolecular interactions - have renewed their interest in water-mediated non-covalent interactions. These two groups offer complementary expertise that, if harnessed, offer to accelerate our understanding of aqueous supramolecular chemistry and water writ large. This Review summarizes the state-of-the-art of the two fields, and highlights where there is latent chemical space for collaborative exploration by the two groups.

Organic Chemistry and Biology: Chemical Biology Through the Eyes of Collaboration

PubMed Central

Hruby, Victor J.

2011-01-01

From a scientific perspective, efforts to understand biology including what constitutes health and disease has become a chemical problem. However, chemists and biologists “see” the problems of understanding biology from different perspectives, and this has retarded progress in solving the problems especially as they relate to health and disease. This suggests that close collaboration between chemists and biologists is not only necessary but essential for progress in both the biology and chemistry that will provide solutions to the global questions of biology. This perspective has directed my scientific efforts for the past 45 years, and in this overview I provide my perspective of how the applications of synthetic chemistry, structural design, and numerous other chemical principles have intersected in my collaborations with biologists to provide new tools, new science, and new insights that were only made possible and fruitful by these collaborations. PMID:20000552

Site Redistribution, Partial Frozen-in Defect Chemistry, and Electrical Properties of Ba1-x(Zr,Pr)O3-δ.

PubMed

Antunes, Isabel; Mikhalev, Sergey; Mather, Glenn Christopher; Kharton, Vladislav Vadimovich; Figueiras, Fábio Gabriel; Alves, Adriana; Rodrigues, Joana; Correia, Maria Rosário; Frade, Jorge Ribeiro; Fagg, Duncan Paul

2016-09-06

Changes in nominal composition of the perovskite (ABO3) solid solution Ba1-x(Zr,Pr)O3-δ and adjusted firing conditions at very high temperatures were used to induce structural changes involving site redistribution and frozen-in point defects, as revealed by Raman and photoluminescence spectroscopies. Complementary magnetic measurements allowed quantification of the reduced content of Pr. Weak dependence of oxygen stoichiometry with temperature was obtained by coulometric titration at temperatures below 1000 °C, consistent with a somewhat complex partial frozen-in defect chemistry. Electrical conductivity measurements combined with transport number and Seebeck coefficient measurements showed prevailing electronic transport and also indicated trends expected for partial frozen-in conditions. Nominal Ba deficiency and controlled firing at very high temperatures allows adjustment of structure and partial frozen-in defect chemistry, opening the way to engineer relevant properties for high-temperature electrochemical applications.

Elaboration of copper-oxygen mediated C-H activation chemistry in consideration of future fuel and feedstock generation.

PubMed

Lee, Jung Yoon; Karlin, Kenneth D

2015-04-01

To contribute solutions to current energy concerns, improvements in the efficiency of dioxygen mediated C-H bond cleavage chemistry, for example, selective oxidation of methane to methanol, could minimize losses in natural gas usage or produce feedstocks for fuels. Oxidative C-H activation is also a component of polysaccharide degradation, potentially affording alternative biofuels from abundant biomass. Thus, an understanding of active-site chemistry in copper monooxygenases, those activating strong C-H bonds is briefly reviewed. Then, recent advances in the synthesis-generation and study of various copper-oxygen intermediates are highlighted. Of special interest are cupric-superoxide, Cu-hydroperoxo and Cu-oxy complexes. Such investigations can contribute to an enhanced future application of C-H oxidation or oxygenation processes using air, as concerning societal energy goals. Copyright © 2015 Elsevier Ltd. All rights reserved.

Chemical research projects office: An overview and bibliography, 1975-1980

NASA Technical Reports Server (NTRS)

Kourtides, D. A.; Heimbuch, A. H.; Parker, J. A.

1980-01-01

The activities of the Chemical Research Projects Office at Ames Research Center, Moffett Field, California are reported. The office conducts basic and applied research in the fields of polymer chemistry, computational chemistry, polymer physics, and physical and organic chemistry. It works to identify the chemical research and technology required for solutions to problems of national urgency, synchronous with the aeronautic and space effort. It conducts interdisciplinary research on chemical problems, mainly in areas of macromolecular science and fire research. The office also acts as liaison with the engineering community and assures that relevant technology is made available to other NASA centers, agencies, and industry. Recent accomplishments are listed in this report. Activities of the three research groups, Polymer Research, Aircraft Operating and Safety, and Engineering Testing, are summarized. A complete bibliography which lists all Chemical Research Projects Office publications, contracts, grants, patents, and presentations from 1975 to 1980 is included.

Collaborative routes to clarifying the murky waters of aqueous supramolecular chemistry

NASA Astrophysics Data System (ADS)

Cremer, Paul S.; Flood, Amar H.; Gibb, Bruce C.; Mobley, David L.

2018-01-01

On planet Earth, water is everywhere: the majority of the surface is covered with it; it is a key component of all life; its vapour and droplets fill the lower atmosphere; and even rocks contain it and undergo geomorphological changes because of it. A community of physical scientists largely drives studies of the chemistry of water and aqueous solutions, with expertise in biochemistry, spectroscopy and computer modelling. More recently, however, supramolecular chemists -- with their expertise in macrocyclic synthesis and measuring supramolecular interactions -- have renewed their interest in water-mediated non-covalent interactions. These two groups offer complementary expertise that, if harnessed, offer to accelerate our understanding of aqueous supramolecular chemistry and water writ large. This Review summarizes the state-of-the-art of the two fields, and highlights where there is latent chemical space for collaborative exploration by the two groups.

All-inorganic Germanium nanocrystal films by cationic ligand exchange

DOE PAGES

Wheeler, Lance M.; Nichols, Asa W.; Chernomordik, Boris D.; ...

2016-01-21

In this study, we introduce a new paradigm for group IV nanocrystal surface chemistry based on room temperature surface activation that enables ionic ligand exchange. Germanium nanocrystals synthesized in a gas-phase plasma reactor are functionalized with labile, cationic alkylammonium ligands rather than with traditional covalently bound groups. We employ Fourier transform infrared and 1H nuclear magnetic resonance spectroscopies to demonstrate the alkylammonium ligands are freely exchanged on the germanium nanocrystal surface with a variety of cationic ligands, including short inorganic ligands such as ammonium and alkali metal cations. This ionic ligand exchange chemistry is used to demonstrate enhanced transport inmore » germanium nanocrystal films following ligand exchange as well as the first photovoltaic device based on an all-inorganic germanium nanocrystal absorber layer cast from solution. This new ligand chemistry should accelerate progress in utilizing germanium and other group IV nanocrystals for optoelectronic applications.« less

Synthesis and luminescence properties of iridium(III) azide- and triazole-bisterpyridine complexes.

PubMed

Goldstein, Daniel C; Peterson, Joshua R; Cheng, Yuen Yap; Clady, Raphael G C; Schmidt, Timothy W; Thordarson, Pall

2013-07-26

We describe here the synthesis of azide-functionalised iridium(III) bisterpyridines using the "chemistry on the complex" strategy. The resulting azide-complexes are then used in the copper(I)-catalysed azide-alkyne Huisgen 1,3-dipolar cycloaddition "click chemistry" reaction to from the corresponding triazole-functionalised iridium(III) bisterpyridines. The photophysical characteristics, including lifetimes, of these compounds were also investigated. Interestingly, oxygen appears to have very little effect on the lifetime of these complexes in aqueous solutions. Unexpectedly, sodium ascorbate acid appears to quench the luminescence of triazole-functionalised iridium(III) bisterpyridines, but this effect can be reversed by the addition of copper(II) sulfate, which is known to oxidize ascorbate under aerobic conditions. The results demonstrate that iridium(III) bisterpyridines can be functionalized for use in "click chemistry" facilitating the use of these photophysically interesting complexes in the modification of polymers or surfaces, to highlight just two possible applications.

Expression of Geochemical Controls on Water Quality in Loch Vale, Rocky Mountain National Park

NASA Astrophysics Data System (ADS)

Podzorski, H.; Navarre-Sitchler, A.; Stets, E.; Clow, D. W.

2017-12-01

Relationships between concentrations of rock weathering products and discharge provide insight into the interactions between climate and solute dynamics. This concentration-discharge (C-Q) relationship is especially interesting in high alpine regions, due to their susceptibility to changes in the timing and magnitude of snowmelt. Previous studies looking at C-Q relationships have concluded that concentrations of conservative solutes remain relatively constant as discharge varies; however, these results may be due to relatively small sample sizes, especially at higher discharge values. Using water chemistry data collected regularly by the U.S. Geological Survey from Loch Vale, a high-elevation catchment in Rocky Mountain National Park, C-Q relationships were examined to determine possible geochemical controls on stream solute concentrations. A record of over 20 years of C-Q data resulted in a pattern that shows little variation in conservative solute concentrations during base flow and larger variations in concentrations around peak discharge. This observed pattern is consistent with accumulation of solutes in pore water during base flow, which are then flushed out and diluted by snowmelt. Further evidence of this flushing out mechanism is found in patterns of hysteresis that are present in annual C-Q relationships. Before peak discharge, concentrations of weathering products are higher than after peak discharge at similar values of discharge. Based on these observations, we hypothesize that the geochemical processes controlling stream chemistry vary by season. During the winter, solute concentrations are transport-limited due to slow subsurface flushing resulting in concentrations that are effectively constant and close to equilibrium. During the spring and summer, concentrations drop sharply after peak discharge due to a combination of dilution and reaction-limited processes under conditions with faster subsurface flow and continued snowmelt. This study provides insight into seasonal geochemical controls on conservative solute concentrations that can be overlooked with small, or seasonally biased, data sets.

Mechanism of Zn Insertion into Nanostructured δ-MnO 2 : A Nonaqueous Rechargeable Zn Metal Battery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, Sang-Don; Kim, Soojeong; Li, Dongguo

2017-05-19

Unlike the more established lithium-ion based energy storage chemistries, the complex intercalation chemistry of multivalent cations in a host lattice is not well understood, especially the relationship between the intercalating species solution chemistry and the prevalence and type of side reactions. Among multivalent metals, a promising model system can be based on nonaqueous Zn2+ ion chemistry. Several examples of these systems support the use of a Zn metal anode, and reversible intercalation cathodes have been reported. This study utilizes a combination of analytical tools to probe the chemistry of a nanostructured delta-MnO2 cathode in association with a nonaqueous acetonitrile-Zn(TFSI)(2) electrolytemore » and a Zn metal anode. As many of the issues related to understanding a multivalent battery relate to the electrolyte electrode interface, the high surface area of a nanostructured cathode provides a significant interface between the electrolyte and cathode host that maximizes the spectroscopic signal of any side reactions or minor mechanistic pathways. Numerous factors affecting capacity fade and issues associated with the second phase formation including Mn dissolution in heavily cycled Zn/delta-MnO2 cells are presented including dramatic mechanistic differences in the storage mechanism of this couple when compared to similar aqueous electrolytes are noted.« less

Connecting the solution chemistry of PbI2 and MAI: a cyclodextrin-based supramolecular approach to the formation of hybrid halide perovskites.

PubMed

Masi, Sofia; Aiello, Federica; Listorti, Andrea; Balzano, Federica; Altamura, Davide; Giannini, Cinzia; Caliandro, Rocco; Uccello-Barretta, Gloria; Rizzo, Aurora; Colella, Silvia

2018-03-28

The evolution from solvated precursors to hybrid halide perovskite films dictates most of the photophysical and optoelectronic properties of the final polycrystalline material. Specifically, the complex equilibria and the importantly different solubilities of lead iodide (PbI 2 ) and methylammonium iodide (MAI) induce inhomogeneous crystal growth, often leading to a defect dense film showing non-optimal optoelectronic properties and intrinsic instability. Here, we explore a supramolecular approach based on the use of cyclodextrins (CDs) to modify the underlying solution chemistry. The peculiar phenomenon demonstrated is a tunable complexation between different CDs and MA + cations concurrent to an out of cage PbI 2 intercalation, representing the first report of a connection between the solvation equilibria of the two perovskite precursors. The optimal conditions in terms of CD cavity size and polarity translate to a neat enhancement of PbI 2 solubility in the reaction media, leading to an equilibration of the availability of the precursors in solution. The macroscopic result of this is an improved nucleation process, leading to a perovskite material with higher crystallinity, better optical properties and improved moisture resistance. Remarkably, the use of CDs presents a great potential for a wide range of device-related applications, as well as for the development of tailored composite materials.

Colloid-Mediated Transport of Pharmaceutical and Personal Care Products through Porous Media

NASA Astrophysics Data System (ADS)

Xing, Yingna; Chen, Xijuan; Chen, Xin; Zhuang, Jie

2016-10-01

Pharmaceutical and personal care products (PPCPs) enter soils through reclaimed water irrigation and biosolid land applications. Colloids, such as clays, that are present in soil may interact with PPCPs and thus affect their fate and transport in the subsurface environment. This study addresses the influence of soil colloids on the sorption and transport behaviors of PPCPs through laboratory column experiments. Results show that the affinities of PPCPs for colloids vary with their molecular chemistry and solution ionic strength. The presence of colloids promotes the breakthrough of ciprofloxacin (over 90% sorbed on colloids) from ~4% to 30-40%, and the colloid-facilitated effect was larger at lower ionic strength (e.g., 2 mM). In comparison, the net effect of colloids on the transport of tetracycline (~50% sorbed on colloids) could be facilitation or inhibition, depending on solution chemistry. This dual effect of colloids is primarily due to the opposite response of migration of dissolved and colloid-bound tetracycline to the change in solution ionic strength. Colloids could also facilitate the transport of ibuprofen (~10% sorbed on colloids) by ~50% due likely to exclusion of dispersion pathways by colloid straining. This study suggests that colloids are significant carriers or transport promoters of some PPCPs in the subsurface environment and could affect their off-site environmental risks.

Colloid-Mediated Transport of Pharmaceutical and Personal Care Products through Porous Media

PubMed Central

Xing, Yingna; Chen, Xijuan; Chen, Xin; Zhuang, Jie

2016-01-01

Pharmaceutical and personal care products (PPCPs) enter soils through reclaimed water irrigation and biosolid land applications. Colloids, such as clays, that are present in soil may interact with PPCPs and thus affect their fate and transport in the subsurface environment. This study addresses the influence of soil colloids on the sorption and transport behaviors of PPCPs through laboratory column experiments. Results show that the affinities of PPCPs for colloids vary with their molecular chemistry and solution ionic strength. The presence of colloids promotes the breakthrough of ciprofloxacin (over 90% sorbed on colloids) from ~4% to 30–40%, and the colloid-facilitated effect was larger at lower ionic strength (e.g., 2 mM). In comparison, the net effect of colloids on the transport of tetracycline (~50% sorbed on colloids) could be facilitation or inhibition, depending on solution chemistry. This dual effect of colloids is primarily due to the opposite response of migration of dissolved and colloid-bound tetracycline to the change in solution ionic strength. Colloids could also facilitate the transport of ibuprofen (~10% sorbed on colloids) by ~50% due likely to exclusion of dispersion pathways by colloid straining. This study suggests that colloids are significant carriers or transport promoters of some PPCPs in the subsurface environment and could affect their off-site environmental risks. PMID:27734948

Synthesis of Ge-nanoparticles in organic solution

NASA Astrophysics Data System (ADS)

Pugsley, Andrew James

Much interest is focused on the synthesis of semiconductor particles from organic solution, in order to provide luminescent tracers for biological assays. However, group IV semiconductors have been largely neglected be cause of the lack of suitable nanoparticle formation reactions by solution-phase chemistries. A potentially useful new route to solution-based synthesis of nanocrystalline-Si,Ge involves the reaction between Zintl phases (NaSi, Mg 2Ge) that formally contain anionic semiconducting group species (Si-, Ge4-) and liquid phase SiCU, GeCU, etc. Luminescent nanoparticles formed by these reactions in organic solvents (e.g. diglyme) have been decribed in work from the Kauzlarich group at UC Davis (California, USA). The aim of this project has been to characterise the structural chemistry and luminescent properties of the products of the reaction, as well as following the course of the reaction in situ via synchrotron measurements. The product of the reaction has been characterised by TEM and x-ray absorption spectroscopy as well as other techniques. In order to analyse the x-ray absorption spectroscopy data, a number of model compounds have been studied, including the precursor material which was previously uncharacterised by this technique. An in situ reaction cell has been designed and built and used at a number of synchrotron beamlines to follow the course of the reaction. It has been found that the presence of even low concentrations of water can greatly affect the formation reaction, this is described herein.

One-Dimensional Transport with Equilibrium Chemistry (OTEQ) - A Reactive Transport Model for Streams and Rivers

USGS Publications Warehouse

Runkel, Robert L.

2010-01-01

OTEQ is a mathematical simulation model used to characterize the fate and transport of waterborne solutes in streams and rivers. The model is formed by coupling a solute transport model with a chemical equilibrium submodel. The solute transport model is based on OTIS, a model that considers the physical processes of advection, dispersion, lateral inflow, and transient storage. The equilibrium submodel is based on MINTEQ, a model that considers the speciation and complexation of aqueous species, acid-base reactions, precipitation/dissolution, and sorption. Within OTEQ, reactions in the water column may result in the formation of solid phases (precipitates and sorbed species) that are subject to downstream transport and settling processes. Solid phases on the streambed may also interact with the water column through dissolution and sorption/desorption reactions. Consideration of both mobile (waterborne) and immobile (streambed) solid phases requires a unique set of governing differential equations and solution techniques that are developed herein. The partial differential equations describing physical transport and the algebraic equations describing chemical equilibria are coupled using the sequential iteration approach. The model's ability to simulate pH, precipitation/dissolution, and pH-dependent sorption provides a means of evaluating the complex interactions between instream chemistry and hydrologic transport at the field scale. This report details the development and application of OTEQ. Sections of the report describe model theory, input/output specifications, model applications, and installation instructions. OTEQ may be obtained over the Internet at http://water.usgs.gov/software/OTEQ.

A computer model for one-dimensional mass and energy transport in and around chemically reacting particles, including complex gas-phase chemistry, multicomponent molecular diffusion, surface evaporation, and heterogeneous reaction

NASA Technical Reports Server (NTRS)

Cho, S. Y.; Yetter, R. A.; Dryer, F. L.

1992-01-01

Various chemically reacting flow problems highlighting chemical and physical fundamentals rather than flow geometry are presently investigated by means of a comprehensive mathematical model that incorporates multicomponent molecular diffusion, complex chemistry, and heterogeneous processes, in the interest of obtaining sensitivity-related information. The sensitivity equations were decoupled from those of the model, and then integrated one time-step behind the integration of the model equations, and analytical Jacobian matrices were applied to improve the accuracy of sensitivity coefficients that are calculated together with model solutions.

X-ray photoemission analysis of chemically modified TlBr surfaces for improved radiation detectors

DOE PAGES

Nelson, A. J.; Voss, L. F.; Beck, P. R.; ...

2013-01-12

We subjected device-grade TlBr to various chemical treatments used in room temperature radiation detector fabrication to determine the resulting surface composition and electronic structure. As-polished TlBr was treated separately with HCl, SOCl 2, Br:MeOH and HF solutions. High-resolution photoemission measurements on the valence band electronic structure and Tl 4f, Br 3d, Cl 2p and S 2p core lines were used to evaluate surface chemistry and shallow heterojunction formation. Surface chemistry and valence band electronic structure were correlated with the goal of optimizing the long-term stability and radiation response.

X-ray photoemission analysis of chemically modified TlBr surfaces for improved radiation detectors

NASA Astrophysics Data System (ADS)

Nelson, A. J.; Voss, L. F.; Beck, P. R.; Graff, R. T.; Conway, A. M.; Nikolic, R. J.; Payne, S. A.; Lee, J.-S.; Kim, H.; Cirignano, L.; Shah, K.

2013-04-01

Device-grade TlBr was subjected to various chemical treatments used in room temperature radiation detector fabrication to determine the resulting surface composition and electronic structure. As-polished TlBr was treated separately with HCl, SOCl2, Br:MeOH, and HF solutions. High-resolution photoemission measurements on the valence band electronic structure and Tl 4f, Br 3d, Cl 2p, and S 2p core lines were used to evaluate surface chemistry and shallow heterojunction formation. Surface chemistry and valence band electronic structure were correlated with the goal of optimizing the long-term stability and radiation response.

Simulating How a Virus Spreads through a Population: An Introduction to Acid-Base Chemistry in the Organic Chemistry Laboratory

NASA Astrophysics Data System (ADS)

Jarret, Ronald M.

2001-04-01

The traditional lab exercise that achieves separation of a mixture of 4-aminoacetophenone and benzoic acid by chemically active extraction has been expanded to include two exercises. First, students provide input on condition selections. This is based on the pooling of data from student observations of the solubility-miscibility behavior of 4-aminoacetophenone, benzoic acid, sodium benzoate, and various solvents and aqueous solutions. Second, students participate in an exercise that uses materials from the extraction experiment to simulate how a virus spreads through a population. The additional mini-exercises promote student participation and reinforce the concepts of the extraction lab.

The chemistry of peroxovanadium compounds relevant to insulin mimesis.

PubMed

Shaver, A; Ng, J B; Hall, D A; Posner, B I

The inorganic coordination chemistry of peroxovanadium compounds relevant to insulin mimesis is reviewed. The structure and kinetic reactivity of solutions of vanadate anion, vanadyl complexes and peroxovanadate complexes are briefly compared. Peroxovanadium compounds contain an oxo group, one or two peroxo ligands (O2(2-)) and an ancillary ligand which is usually bidentate. These compounds approximate a trigonal bipyramidal structure which can be divided conceptually into a polar 'oxo' half and a relatively non-polar organic half. This presents a number of interesting design variations which are discussed with respect to the development of a rudimentary structure-activity correlation of insulin mimetic ability.

Boost-phase discrimination research activities

NASA Technical Reports Server (NTRS)

Cooper, David M.; Deiwert, George S.

1989-01-01

Theoretical research in two areas was performed. The aerothermodynamics research focused on the hard-body and rocket plume flows. Analytical real gas models to describe finite rate chemistry were developed and incorporated into the three-dimensional flow codes. New numerical algorithms capable of treating multi-species reacting gas equations and treating flows with large gradients were also developed. The computational chemistry research focused on the determination of spectral radiative intensity factors, transport properties and reaction rates. Ab initio solutions to the Schrodinger equation provided potential energy curves transition moments (radiative probabilities and strengths) and potential energy surfaces. These surfaces were then coupled with classical particle reactive trajectories to compute reaction cross-sections and rates.

Development and application of the GIM code for the Cyber 203 computer

NASA Technical Reports Server (NTRS)

Stainaker, J. F.; Robinson, M. A.; Rawlinson, E. G.; Anderson, P. G.; Mayne, A. W.; Spradley, L. W.

1982-01-01

The GIM computer code for fluid dynamics research was developed. Enhancement of the computer code, implicit algorithm development, turbulence model implementation, chemistry model development, interactive input module coding and wing/body flowfield computation are described. The GIM quasi-parabolic code development was completed, and the code used to compute a number of example cases. Turbulence models, algebraic and differential equations, were added to the basic viscous code. An equilibrium reacting chemistry model and implicit finite difference scheme were also added. Development was completed on the interactive module for generating the input data for GIM. Solutions for inviscid hypersonic flow over a wing/body configuration are also presented.

Maple syrup-production, composition, chemistry, and sensory characteristics.

PubMed

Perkins, Timothy D; van den Berg, Abby K

2009-01-01

Maple syrup is made from sap exuded from stems of the genus Acer during the springtime. Sap is a dilute solution of primarily water and sucrose, with varying amounts of amino and organic acids and phenolic substances. When concentrated, usually by heating, a series of complex reactions produce a wide variety of flavor compounds that vary due to processing and other management factors, seasonal changes in sap chemistry, and microbial contamination. Color also forms during thermal evaporation. Flavor and color together are the primary factors determining maple syrup grade, and syrup can range from very light-colored and delicate-flavored to very dark-colored and strong-flavored.

Soil mineralogy and chemistry on Mars - Possible clues from salts and clays in SNC meteorites

NASA Technical Reports Server (NTRS)

Gooding, James L.

1992-01-01

If the shergottite, nakhlite, and chassignite (SNC) meteorites' parent planet is Mars, then the aqueous precipitates found in them imply that oxidizing, water-based solutions may have been chemically active on that planet over the past 200-1300 million yrs. It is suggested that the mixture of aqueous precipitates found in the SNCs furnish a self-consistent model for the bulk elemental composition of surface sediments at the Viking Lander sites. Further mineralogical and stable-isotope studies of the secondary minerals may establish the limits for biological activity over the last 1300 million years of Mars' water-based chemistry.

The Effects of Air-Cooled Blast Furnace Slag (ACBFS) Aggregate on the Chemistry of Pore Solution and the Interfacial Transition Zone

NASA Astrophysics Data System (ADS)

Panchmatia, Parth

Numerous laboratory and field studies have demonstrated that concrete incorporating air cooled blast furnace slag (ACBFS) aggregate showed a higher degree of infilling of voids with ettringite as opposed to concrete prepared using naturally mined carbonate aggregates when exposed to similar environmental conditions. This observation prompted some to link the deterioration observed in the ACBFS aggregate concrete structures to the compromised freeze-thaw resistance due to infilling of air voids. Concerns about the release of sulfur from ACBFS aggregate into the pore solution of concrete had been presented as the reason for the observed ettringite deposits in the air voids. However, literature quantifying the influence of ACBFS aggregate on the chemistry of the pore solution of concrete is absent. Therefore, the main purpose of this research was to quantify the effects of ACBFS aggregate on the chemistry of the pore solution of mortars incorporating them. Coarse and crushed ACBFS aggregates were submerged in artificial pore solutions (APSs) representing pore solutions of 3-day, 7-day, and 28-day hydrated plain, binary, and ternary paste systems. The change in the chemistry of these artificial pore solutions was recorded to quantify the chemical contribution of ACBFS aggregate to the pore solution of concrete. It was observed that the sulfate concentration of all APSs increased once they were in contact with either coarse or crushed ACBFS aggregate. After 28 days of contact, the increase in sulfate concentration of the APSs ranged from 4.85 - 12.23 mmol/L and 14.21 - 16.87 mmol/L for contact with coarse and crushed ACBFS aggregate, respectively. More than 40% of the total sulfate that was released by the ACBFS aggregate occurred during the first 72 hours (3 days) of its contact with the APSs. There was little or no difference in the amount of sulfate released from ACBFS aggregate in the different types of APSs. In other words, the type of binder solution from which pore solution was extracted had no effect on the amount of sulfate that was released when it was in contact with ACBFS aggregate. The relatively quick release of sulfur from ACBFS aggregate into the APSs prompted investigation of the chemical composition of the pore solution of mortar (at early stages of hydration) incorporating ACBFS aggregate. The chemical composition of the pore solutions obtained from mortars prepared using ACBFS aggregate and plain and binary paste matrices was compared those of mortars prepared using Ottawa sand and plain and binary paste matrices. After 7 days of hydration, the sulfur (S) concentration of the pore solution extracted from mortars prepared using ACBFS aggregate was 3.4 - 5.6 times greater than that obtained from corresponding mortars (i.e. mortars with the same paste matrix) prepared using Ottawa sand. Binary mortars containing fly ash (FA) showed the lowest S content after 7 days of hydration amongst all mortars prepared using ACBFS aggregate. On the other hand, binary mortars prepared using slag cement (SC) and ACBFS aggregate had the highest S concentration after 7 days of hydration. These effects on the S concentration in the pore solutions can be explained by the difference in the chemical makeup of the binders, and not because of different rate of release of S from ACBFS into the pore solution. In addition, TGA analysis of 7-day hydrated mortars revealed that the ettringite, monosulfate, and calcium hydroxide content was lower in mortars prepared using ACBFS aggregate as opposed to those prepared using Ottawa sand. This could be because of the low degree of hydration in mortars with ACBFS aggregate because of the high sulfate concentration in its pore solution. The properties of the interfacial transition zone (ITZ), i.e. the zone in the vicinity of the aggregate surface, depends on the property of the aggregate such as its porosity and texture. Therefore, it is expected that the properties of ITZ around the ACBFS particle, which is porous and proven to contribute sulfate, be different from the ITZ around the naturally mined siliceous aggregate. Image analysis conducted on backscattered images obtained using scanning electron microscope revealed that the ITZ of naturally mined siliceous aggregate was more porous compared to the ITZ of ACBFS aggregate. In addition, calcium hydroxide deposits were more frequent and larger in size in the ITZ around siliceous sand than in the case of the ITZ around the ACBFS aggregate.

Atmospheric deposition effects on the chemistry of a stream in Northeastern Georgia

USGS Publications Warehouse

Buell, G.R.; Peters, N.E.

1988-01-01

The quantity and quality of precipitation and streamwater were measured from August 1985 through September 1986 in the Brier Creek watershed, a 440-ha drainage in the Southern Blue Ridge Province of northeastern Georgia, to determine stream sensitivity to acidic deposition. Precipitation samples collected at 2 sites had a volume-weighted average pH of 4.40 whereas stream samples collected near the mouth of Brier Creek had a discharge-weighted average pH of 6.70. Computed solute fluxes through the watershed and observed changes in streamwater chemistry during stormflow suggest that cation exchange, mineral weathering, SO42- adsorption by the soil, and groundwater discharge to the stream are probable factors affecting neutralization of precipitation acidity. Net solute fluxes for the watershed indicate that, of the precipitation input, > 99% of the H+, 93% of the NH4+ and NO3-, and 77% of the SO42- were retained. Sources within the watershed yielded base cations, Cl-, and HCO3- and accounted for 84, 47, and 100% of the net transport, respectively. Although streamwater SO42- and NO3- concentrations increased during stormflow, peak concentrations of these anions were much less than average concentrations in the precipitation. This suggests retention of these solutes occurs even when water residence time is short.The quantity and quality of precipitation and streamwater were measured from August 1985 through September 1986 in the Brier Creek watershed, a 440-ha drainage in the Southern Blue Ridge Province of northeastern Georgia, to determine stream sensitivity to acidic deposition. Precipitation samples collected at 2 sites had a volume-weighted average pH of 4.40 whereas stream samples collected near the mouth of Brier Creek had a discharge-weighted average pYH of 6.70. Computed solute fluxes through the watershed and observed changes in streamwater chemistry drying stormflow suggest that cation exchange, mineral weathering, SO42- adsorption by the soil, and groundwater discharge to the stream are probable factors affecting neutralization of precipitation acidity. Although streamwater SO42- and NO3- concentrations increased during stormflow, peak concentrations of these anions were much less than average concentrations in the precipitation. This suggests retention of these solutes occurs even when water residence time is short.

A qualitative study of high school students' pre- and post-instructional conceptions in acid-base chemistry

NASA Astrophysics Data System (ADS)

Sheppard, Keith

This study investigated high school students' understanding of acid-base chemistry, prior to and after formal chemistry instruction. Sixteen students enrolled in a regular chemistry course were interviewed three times during the school year; before and after studying the topic of acids and bases and then while conducting a titration using a microcomputer-based laboratory (MBL). Oral, pictorial and graphical data were collected in a variety of acid-base practical tasks. The data were analyzed in two parts; first, common themes, ideas and alternative conceptions that students held were identified; second, profiles of each students were made to determine changes in their conceptions due to instruction. The findings showed that students had considerable difficulty with several areas of acid-base chemistry and did not develop an integrated conceptual understanding of the topic. Students were unable to describe acid-base concepts accurately and revealed a number of alternative conceptions, which remained unchanged by instruction. Specific areas of difficulty included the concepts of pH, neutralization, strength and the theoretical descriptions of acids and bases. Further, most students could not relate the concepts to actual solutions and were unable to describe acid-base phenomena at a sub-microscopic level. Student difficulties stemmed from a lack of understanding of some underlying and fundamental chemistry, such as the nature of chemical change and the particulate nature of matter. A number of factors were identified as contributing to these difficulties, and included the overstuffed nature of introductory chemistry itself, the emphasis in instruction on solving numerical problems and the dominant role played by the textbook. Further, the conceptual density of acid-base chemistry, the confusing nature of acid-base terminology and the lack of agreement about what material should be included in the chemistry curriculum were viewed as problematic. The study calls for a shift in introductory chemistry, from coverage of material to an emphasis on conceptual understanding, and suggests the use of more appropriate teaching strategies, the use of modern technologies, the inclusion of alternative modes of assessment and a re-evaluation of the chemistry introduced into the topic of acids and bases.

Humic acid facilitates the transport of ARS-labeled hydroxyapatite nanoparticles in iron oxyhydroxide-coated sand

USDA-ARS?s Scientific Manuscript database

Hydroxyapatite nanoparticles (nHAP) have been widely used to remediate soil and wastewater contaminated with metals and radionuclides. However, our understanding of nHAP transport and fate is limited in natural environments that exhibit significant variability in solid and solution chemistry. The tr...

Complexometric Determination of Mercury Based on a Selective Masking Reaction

ERIC Educational Resources Information Center

Romero, Mercedes; Guidi, Veronica; Ibarrolaza, Agustin; Castells, Cecilia

2009-01-01

In the first analytical chemistry course, students are introduced to the concepts of equilibrium in water solutions and classical (non-instrumental) analytical methods. Our teaching experience shows that "real samples" stimulate students' enthusiasm for the laboratory work. From this diagnostic, we implemented an optional activity at the end of…

Chemistry for Kids: What Do Chemists Do? A Program for Grades 1-3.

ERIC Educational Resources Information Center

Umland, Jean B.

1985-01-01

Proposes a simple solution to the problem of expressing graphically absolute configuration, racemic character, and relative configuration in molecules. As demonstrated by several examples, the proposed convention brings added clarity and simplicity to structural drawings and renders graphic displays of chiral molecules as explicit and information…

Transport and retention of surfactant- and polymer-stabilized engineered silver nanoparticles in silicate-dominated aquifer material

USDA-ARS?s Scientific Manuscript database

Packed column experiments were conducted to investigate the transport and blocking behavior of surfactant- and polymer-stabilized engineered silver nanoparticles (Ag-ENPs) in saturated natural aquifer material with varying silt and clay content, background solution chemistry, and flow velocity. Brea...

Nutrient depletion from rhizosphere solution by maize grown in soil with long-term compost amendment

USDA-ARS?s Scientific Manuscript database

Improved understanding of rhizosphere chemistry will enhance our ability to model nutrient dynamics and on a broader scale, to develop effective management strategies for applied plant nutrients. With a controlled-climate study, we evaluated in situ changes in macro-nutrient concentrations in the rh...

Nutrient sampling slam: high resolution surface-water sampling in streams reveals patterns in groundwater chemistry and flow paths

EPA Science Inventory

The groundwater–surface water interface (GSWI), consisting of shallow groundwater adjacent to stream channels, is a hot spot for nitrogen removal processes, a storage zone for other solutes, and a target for restoration activities. Characterizing groundwater-surface water intera...

Evaporation rate-based selection of supramolecular chirality.

PubMed

Hattori, Shingo; Vandendriessche, Stefaan; Koeckelberghs, Guy; Verbiest, Thierry; Ishii, Kazuyuki

2017-03-09

We demonstrate the evaporation rate-based selection of supramolecular chirality for the first time. P-type aggregates prepared by fast evaporation, and M-type aggregates prepared by slow evaporation are kinetic and thermodynamic products under dynamic reaction conditions, respectively. These findings provide a novel solution reaction chemistry under the dynamic reaction conditions.

The Redox Chemistry of Metallophthalocyanines in Solution

DTIC Science & Technology

1992-05-19

role if they have donor characteristics. Thus the perchlorate and hexafluorophosphate ions are usually regarded as nondonor species, although this may...Table 2) (and also in the lithium salt, see the following) and is more difficult to reduce because of the net negtive charge [41- --4/9/92 --pcrev

Influence of Inorganic Ions and Aggregation and Adsorption Behaviors of Human Adenovirus

EPA Science Inventory

In this study, influence of solution chemistries to the transport properties (aggregation and attachment behavior) of human adenovirus (HAdV) was investigated. Results showed isoelectric point (IEP) of HAdV in different salt conditions varied minimally, and it ranged from pH 3.5 ...

Robust Structure and Reactivity of Aqueous Arsenous Acid-Platinum(II) Anticancer Complexes**

PubMed Central

Miodragović, Ðenana U.; Quentzel, Jeremy A.; Kurutz, Josh W.; Stern, Charlotte L.; Ahn, Richard W.; Kandela, Irawati; Mazar, Andrew; O’Halloran, Thomas V.

2014-01-01

The first molecular adducts of platinum and arsenic based anticancer drugs - arsenoplatins - show unanticipated structure, substitution chemistry, and cellular cytotoxicity. The PtII-AsIII bonds in these complexes are stable in aqueous solution and strongly influence the lability of the trans ligand. PMID:24038962

Investigations in Marine Chemistry: Salinity II.

ERIC Educational Resources Information Center

Schlenker, Richard M.

Presented is a science activity in which the student investigates methods of calibration of a simple conductivity meter via a hands-on inquiry technique. Conductivity is mathematically compared to salinity using a point slope formula and graphical techniques. Sample solutions of unknown salinity are provided so that the students can sharpen their…

Computer program determines chemical composition of physical system at equilibrium

NASA Technical Reports Server (NTRS)

Kwong, S. S.

1966-01-01

FORTRAN 4 digital computer program calculates equilibrium composition of complex, multiphase chemical systems. This is a free energy minimization method with solution of the problem reduced to mathematical operations, without concern for the chemistry involved. Also certain thermodynamic properties are determined as byproducts of the main calculations.

Control of Chemical Equilibrium by Solvent: A Basis for Teaching Physical Chemistry of Solutions

ERIC Educational Resources Information Center

Prezhdo, Oleg V.; Craig, Colleen F.; Fialkov, Yuriy; Prezhdo, Victor V.

2007-01-01

The study demonstrates that the solvent present in a system can highly alter and control the chemical equilibrium of a system. The results show that the dipole moment and polarizibility of a system can be highly altered by using different mixed solvents.

Solar chemistry of metal complexes

NASA Astrophysics Data System (ADS)

Gray, H. B.; Maverick, A. W.

1981-12-01

Electronic excited states of certain transition metal complexes undergo oxidation-reduction reactions that store chemical energy. Such reactions have been extensively explored for mononuclear complexes. Two classes of polynuclear species exhibit similar properties, and these complexes are now being studied as possible homogeneous sensitizer-catalysts for hydrogen production from aqueous solutions.

Determination of Log K[subscript ow] Values for Four Drugs

ERIC Educational Resources Information Center

Harris, Mark F.; Logan, Jennifer L.

2014-01-01

Though many undergraduates are interested in medicine, relatively few experiments related to drug design and development are included in introductory chemistry laboratory courses. In this experiment, aqueous solutions of four different drugs (acetaminophen, caffeine, phenacetin, and sulfanilamide) are extracted using 1-octanol, a mimic of the…

Box-and-Whisker Plots.

ERIC Educational Resources Information Center

Larsen, Russell D.

1985-01-01

Box-and-whisker plots (which give rapid visualization of batches of data) can be effectively used to present diverse collections of data used in traditional first-year chemistry courses. Construction of box-and-whisker plots and their use with bond energy data and data on heats of formation and solution are discussed. (JN)

The surface chemistry of multi-oxide silicates

NASA Astrophysics Data System (ADS)

Oelkers, Eric H.; Golubev, Sergey V.; Chairat, Claire; Pokrovsky, Oleg S.; Schott, Jacques

2009-08-01

The surface chemistry of natural wollastonite, diopside, enstatite, forsterite, and albite in aqueous solutions was characterized using both electrokinetic techniques and surface titrations performed for 20 min in batch reactors. Titrations performed in such reactors allow determination of both proton consumption and metal release from the mineral surface as a function of pH. The compositions, based on aqueous solution analysis, of all investigated surfaces vary dramatically with solution pH. Ca and Mg are preferentially released from the surfaces of all investigated divalent metal silicates at pH less than ˜8.5-10 but preferentially retained relative to silica at higher pH. As such, the surfaces of these minerals are Si-rich and divalent metal poor except in strongly alkaline solutions. The preferential removal of divalent cations from these surfaces is coupled to proton consumption. The number of protons consumed by the preferential removal of each divalent cation is pH independent but depends on the identity of the mineral; ˜1.5 protons are consumed by the preferential removal of each Ca atom from wollastonite, ˜3 protons are consumed by the preferential removal of each Mg or Ca atom from diopside or enstatite, and ˜4 protons are consumed by the preferential removal of each Mg from forsterite. These observations are interpreted to stem from the creation of additional 'internal' adsorption sites by the preferential removal of divalent metal cations which can be coupled to the condensation of partially detached Si. Similarly, Na and Al are preferentially removed from the albite surface at 2 > pH > 11; mass balance calculations suggest that three protons are consumed by the preferential removal of each Al atom from this surface over this entire pH range. Electrokinetic measurements on fresh mineral powders yield an isoelectric point (pH IEP) 2.6, 4.4, 3.0, 4.5, and <1, for wollastonite, diopside, enstatite, forsterite, and albite, respectively, consistent with the predominance of SiO 2 in the surface layer of all of these multi-oxide silicates at acidic pH. Taken together, these observations suggest fundamental differences between the surface chemistry of simple versus multi-oxide minerals including (1) a dependency of the number and identity of multi-oxide silicate surface sites on the aqueous solution composition, and (2) the dominant role of metal-proton exchange reactions on the reactivity of multi-oxide mineral surfaces including their dissolution rate variation with aqueous solution composition.

Cycle chemistry monitoring system as means of improving the reliability of the equipment at the power plants

NASA Astrophysics Data System (ADS)

Yegoshina, O. V.; Voronov, V. N.; Yarovoy, V. O.; Bolshakova, N. A.

2017-11-01

There are many problems in domestic energy at the present that require urgent solutions in the near future. One of these problems - the aging of the main and auxiliary equipment. Wear of equipment is the cause of decrease reliability and efficiency of power plants. Reliability of the equipment are associated with the introduction of cycle chemistry monitoring system. The most damageable equipment’s are boilers (52.2 %), turbines (12.6 %) and heating systems (12.3 %) according to the review of failure rate on the power plants. The most part of the damageability of the boiler is heated surfaces (73.2 %). According to the Russian technical requirements, the monitoring systems are responsible to reduce damageability the boiler heating surfaces and to increase the reliability of the equipment. All power units capacity of over 50 MW are equipped with cycle chemistry monitoring systems in order to maintain water chemistry within operating limits. The main idea of cycle chemistry monitoring systems is to improve water chemistry at power plants. According to the guidelines, cycle chemistry monitoring systems of a single unit depends on its type (drum or once-through boiler) and consists of: 20…50 parameters of on-line chemical analyzers; 20…30 «grab» sample analyses (daily) and about 15…20 on-line monitored operating parameters. The operator of modern power plant uses with many data at different points of steam/water cycle. Operators do not can estimate quality of the cycle chemistry due to the large volume of daily and every shift information and dispersion of data, lack of systematization. In this paper, an algorithm for calculating the quality index developed for improving control the water chemistry of the condensate, feed water and prevent scaling and corrosion in the steam/water cycle.

Presence of Li Clusters in Molten LiCl-Li

PubMed Central

Merwin, Augustus; Phillips, William C.; Williamson, Mark A.; Willit, James L.; Motsegood, Perry N.; Chidambaram, Dev

2016-01-01

Molten mixtures of lithium chloride and metallic lithium are of significant interest in various metal oxide reduction processes. These solutions have been reported to exhibit seemingly anomalous physical characteristics that lack a comprehensive explanation. In the current work, the physical chemistry of molten solutions of lithium chloride and metallic lithium, with and without lithium oxide, was investigated using in situ Raman spectroscopy. The Raman spectra obtained from these solutions were in agreement with the previously reported spectrum of the lithium cluster, Li8. This observation is indicative of a nanofluid type colloidal suspension of Li8 in a molten salt matrix. It is suggested that the formation and suspension of lithium clusters in lithium chloride is the cause of various phenomena exhibited by these solutions that were previously unexplainable. PMID:27145895

Can oral rehydration solution be safely flavored at home?

PubMed

Nijssen-Jordan, C

1997-12-01

To determine the concentration of sodium, potassium, glucose, and osmolality of oral rehydration solutions (ORS) which have been flavored with varying amounts of unsweetened Kool-Aid powder, Jell-O powder, apple juice, or orange juice. Descriptive. Alberta Children's Hospital Chemistry Laboratory. None. Addition of varying amounts of flavoring easily available in all households to commercially available unsweetened ORS. Concentrations of electrolytes, glucose, and osmolality. Addition of fruit juices or flavor powders to commercially produced ORS does alter the electrolyte content and osmolality. When limited amounts of flavoring or juice is added, the osmolality of the solution approaches iso-osmolality. Small amounts of unsweetened Kool-Aid powder, Jell-O powder, and apple or orange juice can be added to oral rehydration solutions without significantly altering electrolyte composition and osmolality.

Computational modeling of chemical reactions and interstitial growth and remodeling involving charged solutes and solid-bound molecules

PubMed Central

Nims, Robert J.; Maas, Steve; Weiss, Jeffrey A.

2014-01-01

Mechanobiological processes are rooted in mechanics and chemistry, and such processes may be modeled in a framework that couples their governing equations starting from fundamental principles. In many biological applications, the reactants and products of chemical reactions may be electrically charged, and these charge effects may produce driving forces and constraints that significantly influence outcomes. In this study, a novel formulation and computational implementation are presented for modeling chemical reactions in biological tissues that involve charged solutes and solid-bound molecules within a deformable porous hydrated solid matrix, coupling mechanics with chemistry while accounting for electric charges. The deposition or removal of solid-bound molecules contributes to the growth and remodeling of the solid matrix; in particular, volumetric growth may be driven by Donnan osmotic swelling, resulting from charged molecular species fixed to the solid matrix. This formulation incorporates the state of strain as a state variable in the production rate of chemical reactions, explicitly tying chemistry with mechanics for the purpose of modeling mechanobiology. To achieve these objectives, this treatment identifies the specific theoretical and computational challenges faced in modeling complex systems of interacting neutral and charged constituents while accommodating any number of simultaneous reactions where reactants and products may be modeled explicitly or implicitly. Several finite element verification problems are shown to agree with closed-form analytical solutions. An illustrative tissue engineering analysis demonstrates tissue growth and swelling resulting from the deposition of chondroitin sulfate, a charged solid-bound molecular species. This implementation is released in the open-source program FEBio (www.febio.org). The availability of this framework may be particularly beneficial to optimizing tissue engineering culture systems by examining the influence of nutrient availability on the evolution of inhomogeneous tissue composition and mechanical properties, the evolution of construct dimensions with growth, the influence of solute and solid matrix electric charge on the transport of cytokines, the influence of binding kinetics on transport, the influence of loading on binding kinetics, and the differential growth response to dynamically loaded versus free-swelling culture conditions. PMID:24558059

Computational modeling of chemical reactions and interstitial growth and remodeling involving charged solutes and solid-bound molecules.

PubMed

Ateshian, Gerard A; Nims, Robert J; Maas, Steve; Weiss, Jeffrey A

2014-10-01

Mechanobiological processes are rooted in mechanics and chemistry, and such processes may be modeled in a framework that couples their governing equations starting from fundamental principles. In many biological applications, the reactants and products of chemical reactions may be electrically charged, and these charge effects may produce driving forces and constraints that significantly influence outcomes. In this study, a novel formulation and computational implementation are presented for modeling chemical reactions in biological tissues that involve charged solutes and solid-bound molecules within a deformable porous hydrated solid matrix, coupling mechanics with chemistry while accounting for electric charges. The deposition or removal of solid-bound molecules contributes to the growth and remodeling of the solid matrix; in particular, volumetric growth may be driven by Donnan osmotic swelling, resulting from charged molecular species fixed to the solid matrix. This formulation incorporates the state of strain as a state variable in the production rate of chemical reactions, explicitly tying chemistry with mechanics for the purpose of modeling mechanobiology. To achieve these objectives, this treatment identifies the specific theoretical and computational challenges faced in modeling complex systems of interacting neutral and charged constituents while accommodating any number of simultaneous reactions where reactants and products may be modeled explicitly or implicitly. Several finite element verification problems are shown to agree with closed-form analytical solutions. An illustrative tissue engineering analysis demonstrates tissue growth and swelling resulting from the deposition of chondroitin sulfate, a charged solid-bound molecular species. This implementation is released in the open-source program FEBio ( www.febio.org ). The availability of this framework may be particularly beneficial to optimizing tissue engineering culture systems by examining the influence of nutrient availability on the evolution of inhomogeneous tissue composition and mechanical properties, the evolution of construct dimensions with growth, the influence of solute and solid matrix electric charge on the transport of cytokines, the influence of binding kinetics on transport, the influence of loading on binding kinetics, and the differential growth response to dynamically loaded versus free-swelling culture conditions.

Online and offline mass spectrometric study of the impact of oxidation and ageing on glyoxal chemistry and uptake onto ammonium sulfate aerosols.

PubMed

Hamilton, Jacqueline F; Baeza-Romero, M Teresa; Finessi, Emanuela; Rickard, Andrew R; Healy, Robert M; Peppe, Salvatore; Adams, Thomas J; Daniels, Mark J S; Ball, Stephen M; Goodall, Iain C A; Monks, Paul S; Borrás, Esther; Muñoz, Amalia

2013-01-01

Recent laboratory and modelling studies have shown that reactive uptake of low molecular weight alpha-dicarbonyls such as glyoxal (GLY) by aerosols is a potentially significant source of secondary organic aerosol (SOA). However, previous studies disagree in the magnitude of the uptake of GLY, the mechanism involved and the physicochemical factors affecting particle formation. In this study, the chemistry of GLY with ammonium sulfate (AS) in both bulk laboratory solutions and in aerosol particles is investigated. For the first time, Aerosol Time of Flight Mass Spectrometry (ATOFMS), a single particle technique, is used together with offline (ESI-MS and LC-MS2) mass spectrometric techniques to investigate the change in composition of bulk solutions of GLY and AS resulting from aqueous photooxidation by OH and from ageing of the solutions in the dark. The mass spectral ions obtained in these laboratory studies were used as tracers of GLY uptake and chemistry in AS seed particles in a series of experiments carried out under dark and natural irradiated conditions at the outdoor European Photo-reactor (EUPHORE). Glyoxal oligomers formed were not detected by the ATOFMS, perhaps due to inefficient absorption at the laser wavelength. However, the presence of organic nitrogen compounds, formed by reaction of GLY with ammonia was confirmed, resulting in an increase in the absorption efficiency of the aerosol, and this increased the number of particles successfully ionised by the ATOFMS. A number of light absorbing organic nitrogen species, including 1H-imidazole, 1H-imidazole-2-carboxaldehyde, 2,2'-bis-imidazole and a glyoxal substituted 2,2'-bisimidazole, previously identified in aqueous laboratory solutions, were also identified in chamber aerosol and formed on atmospherically relevant timescales. An additional compound, predicted to be 1,2,5-oxadiazole, had an enhanced formation rate when the chamber was open and is predicted to be formed via a light activated pathway involving radical oxidation of ammonia to hydroxylamine, followed by subsequent reaction with glyoxal to form an intermediate glyoxime.

Determination of the Corrosive Conditions Present within Aircraft Lap-Splice Joints

NASA Technical Reports Server (NTRS)

Lewis, Karen S.; Kelly, Robert G.; Piascik, Robert S.

1999-01-01

The complexity of airframe structure lends itself to damage resulting from crevice corrosion. Fuselage lap-splice joints are a particularly important structural detail in this regard because of the difficulty associated with detection and measurement of corrosion in these occluded regions. The objective of this work is to develop a laboratory corrosion test protocol to identify the chemistry to which lap joints are exposed and to develop a model of the corrosion within the joints. A protocol for collecting and identifying the chemistry of airframe crevice corrosion has been developed. Capillary electrophoresis (CE) is used to identify the ionic species contained in corrosion product samples removed from fuselage lap splice joints. CE analysis has been performed on over sixty corrosion product samples removed from both civilian and military aircraft. Over twenty different ions have been detected. Measurements of pH of wetted corroded surfaces indicated an alkaline occluded solution. After determining the species present and their relative concentrations, the resultant solution was reproduced in bulk and electrochemical tests were performed to determine the corrosion rate. Electrochemical analyses of the behavior of AA2024-T3 in these solutions gave corrosion rates of up to 250 microns per year (10 mpy). Additional tests have determined the relative importance of each of the detected ions in model solutions used for future predictive tests. The statistically significant ions have been used to create a second generation solution. Laboratory studies have also included exposure tests involving artificial lap joints exposed to various simulated bulk and crevice environments. The extent and morphology of the attack in artificial lap joints has been compared to studies of corroded samples from actual aircraft. Other effects, such as temperature and potential, as well as the impact of the environment on fatigue crack growth have also been studied.

Gaz Phase IR and UV Spectroscopy of Neutral Contact Ion Pairs

NASA Astrophysics Data System (ADS)

Habka, Sana; Brenner, Valerie; Mons, Michel; Gloaguen, Eric

2016-06-01

Cations and anions, in solution, tend to pair up forming ion pairs. They play a crucial role in many fundamental processes in ion-concentrated solutions and living organisms. Despite their importance and vast applications in physics, chemistry and biochemistry, they remain difficult to characterize namely because of the coexistence of several types of pairing in solution. However, an interesting alternative consists in applying highly selective gas phase spectroscopy which can offer new insights on these neutral ion pairs. Our study consists in characterizing contact ion pairs (CIPs) in isolated model systems (M+, Ph-(CH2)n-COO- with M=Li, Na, K, Rb, Cs, and n=1-3), to determine their spectral signatures and compare them to ion pairs in solution. We have used laser desorption to vaporize a solid tablet containing the desired salt. Structural information for each system was obtained by mass-selective, UV and IR laser spectroscopy combined with high level quantum chemistry calculations1. Evidence of the presence of neutral CIPs was found by scanning the π-π* transition of the phenyl ring using resonant two-photon ionization (R2PI). Then, conformational selective IR/UV double resonance spectra were recorded in the CO2- stretch region for each conformation detected. The good agreement between theoretical data obtained at the BSSE-corrected-fullCCSD(T)/dhf-TZVPP//B97-D3/dhf-TZVPP level and experimental IR spectra led us to assign the 3D structure for each ion pair formed. Spectral signatures of (M+, Ph-CH2-COO-) pairs, were assigned to a bidentate CIPs between the alkali cation and the carboxylate group. In the case of (Li+, Ph-(CH2)3-COO-) pairs, the presence of a flexible side chain promotes a cation-π interaction leading to a tridentate O-O-π structure with its unique IR and UV signatures. IR spectra obtained on isolated CIPs were found very much alike the ones published on lithium and sodium acetate in solution2. However, in the case of sodium acetate, solution spectra were assigned to solvent shared pairs. Yet, the striking resemblance with our spectral data raises questions about the type assigned, pointing out that CIPs could be more present in these electrolyte solutions than previously thought. The novelty of the gas phase approach to investigate neutral ion pairs, opens the door for various new spectroscopic studies, paving the way to greater knowledge regarding the properties of ion pairs in many scientific fields. 1. Gloaguen, E.; Mons, M.; Topics in Current Chemistry, 2015, Vol 364, 225-270 2. Rudolph, W.W.; Fischer, D.; Irmer, G.; Dalton Transactions 2014, 43, (8), 3174-3185

Electrospray Charging of Minerals: Surface Chemistry and Applications to High-Velocity Microparticle Impacts

NASA Astrophysics Data System (ADS)

Daly, T.; Call, S.; Austin, D. E.

2010-12-01

Electrospray is a soft ionization technique commonly used to charge large biomolecules; it has, however, also been applied to inorganic compounds. We are extending this technique to mineral microparticles. Electrospray-charged mineral microparticles are interesting in the context of surface science because surface chemistry dictates where and how charge carriers can bond to mineral surfaces. In addition, using electrospray to charge mineral particles allows these particles to be electrostatically accelerated as projectiles in high- and hyper-velocity impacts. Since current techniques for producing high- and hyper-velocity microparticle impacts are largely limited to metal or metal-coated projectiles, using minerals as projectiles is a significant innovation. Electrospray involves three steps: creation of charged droplets containing solute/particles, evaporation and bifurcation of droplets, and desolvation of the solute/particles. An acidified solution is slowly pumped through a needle in a strong DC field, which causes the solution to break into tiny, charged droplets laden with protons. Solvent evaporates from the electrosprayed droplets as they move through the electric field toward a grounded plate, causing the charge on the droplet to increase relative to its mass. When the electrosprayed droplet’s charge becomes such that the droplet is no longer stable, it bifurcates, and each of the resulting droplets carries some of the original droplet’s charge. Evaporation and bifurcation continues until the solute particle is completely desolvated. The result is a protonated solute molecule or particle. We built an instrument that electrosprays particles into vacuum and measures them using an image charge detector. Mineral microparticles were prepared by grinding natural mineral samples to ~2 µm diameter. These microparticles are then added to a 4:1 methanol:water solution to create a 0.005% w/v suspension. The suspension is electrosprayed into vacuum, where the charge detector measures the electrosprayed mineral particles’ speed and charge. Quartz microparticles have been successfully electrosprayed. Variation in quartz microparticles’ charge as a function of pH is being evaluated. In addition, we are studying how to completely desolvate electrosprayed mineral particles. Desolvation is not trivial and often requires more than the passive passage of the droplets from the needle to the grounded plate and into vacuum. We are testing two desolvation methods: a heated beam tube and a heated capillary. Preliminary data suggests we have achieved complete desolvation with a hot beam tube. Although quartz’s surface chemistry is rather unique, successful electrospray of quartz microparticles strongly suggests that other minerals may also be electrosprayed. We are preparing olivine samples for electrospray. In addition, an instrument that creates high-velocity microparticle impacts using electrospray-charged mineral microparticles is being developed. This instrument will not only permit minerals to be used as projectiles, but also allows direction characterization of chemical speciation occurring during microparticle impacts.

Sensing of biologically relevant d-metal ions using a Eu(III)-cyclen based luminescent displacement assay in aqueous pH 7.4 buffered solution.

PubMed

Kotova, Oxana; Comby, Steve; Gunnlaugsson, Thorfinnur

2011-06-28

1·Eu·BPS was developed as a luminescent lanthanide sensor for use in displacement assays for detection of d-metal ions by monitoring the changes in the europium emission, which was quenched for iron(II), with a detection limit of ∼10 pM (0.002 μg L(-1)) for Fe(II) in buffered pH 7.4 solution. This journal is © The Royal Society of Chemistry 2011

Polymerization of beta-amino acids in aqueous solution

NASA Technical Reports Server (NTRS)

Liu, R.; Orgel, L. E.; Bada, J. L. (Principal Investigator)

1998-01-01

We have compared carbonyl diimidazole (CDI) and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDAC) as activating agents for the oligomerization of negatively-charged alpha- and beta-amino acids in homogeneous aqueous solution. alpha-Amino acids can be oligomerized efficiently using CDI, but not by EDAC. beta-Amino acids can be oligomerized efficiently using EDAC, but not by CDI. Aspartic acid, an alpha- and beta-dicarboxylic acid is oligomerized efficiently by both reagents. These results are explained in terms of the mechanisms of the reactions, and their relevance to prebiotic chemistry is discussed.

Disulfide exchange in hydrogen-bonded cyclic assemblies: stereochemical self-selection by double dynamic chemistry.

PubMed

ten Cate, A Tessa; Dankers, Patricia Y W; Sijbesma, Rint P; Meijer, E W

2005-07-22

Stereoselective cyclization of cystine-based bifunctional 2-ureido-4[1H]-pyrimidinone derivatives in CDCl(3) solutions was demonstrated by (1)H NMR spectroscopy. Thiolate-catalyzed disulfide exchange in solution led to the equilibration of different diastereomers of 1. At low concentrations, where formation of cyclic assemblies is the dominant mode of association, the molecules act as their own template. At these concentrations the meso diastereomer is formed preferentially, indicating a higher stability of its cyclic assemblies under the applied conditions, in comparison to the other diastereomers.

Polynuclear Speciation of Trivalent Cations near the Surface of an Electrolyte Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bera, Mrinal K.; Antonio, Mark R.

Despite long-standing efforts, there is no agreed upon structural model for electrolyte solutions at air-liquid interfaces. We report the simultaneous detection of the near-surface and bulk coordination environments of a trivalent metal cation (europium) in an aqueous solution by use of X-ray absorption spectroscopy. Within the first few nanometers of the liquid surface, the cations exhibit oxygen coordination typical of inner-sphere hydration of an aquated Eu3+ cation. Beyond that, outer-sphere ion-ion correlations are observed that are otherwise not present in the bulk electrolyte. The combination of near-surface and bulk sensitivities to probe metal ion speciation in electrolyte solutions is achievedmore » by detecting electron-yield and X-ray fluorescence signals from an inverted pendant drop. The results provide new knowledge about the near-surface chemistry of aqueous solutions of relevance to aerosols and ion transport processes in chemical separations and biological systems.« less

Influence of corrosive solutions on microhardness and chemistry of magnesium oxide /001/ surfaces

NASA Technical Reports Server (NTRS)

Ishigaki, H.; Miyoshi, K.; Buckley, D. H.

1982-01-01

X-ray photoelectron spectroscopy analyses and hardness experiments were conducted on cleaved magnesium oxide /001/ surfaces. The magnesium oxide bulk crystals were cleaved to specimen size along the /001/ surface, and indentations were made on the cleaved surface in corrosive solutions containing HCl, NaOH, or HNO3 and in water without exposing the specimen to any other environment. The results indicated that chloride (such as MgCl2) and sodium films are formed on the magnesium oxide surface as a result of interactions between an HCl-containing solution and a cleaved magnesium oxide surface. The chloride films soften the magnesium oxide surface. In this case microhardness is strongly influenced by the pH value of the solution. The lower the pH, the lower the microhardness. Sodium films, which are formed on the magnesium oxide surface exposed to an NaOH containing solution, do not soften the magnesium oxide surface.

An investigation of the effects of relevant samples and a comparison of verification versus discovery based lab design

NASA Astrophysics Data System (ADS)

Rieben, James C., Jr.

This study focuses on the effects of relevance and lab design on student learning within the chemistry laboratory environment. A general chemistry conductivity of solutions experiment and an upper level organic chemistry cellulose regeneration experiment were employed. In the conductivity experiment, the two main variables studied were the effect of relevant (or "real world") samples on student learning and a verification-based lab design versus a discovery-based lab design. With the cellulose regeneration experiment, the effect of a discovery-based lab design vs. a verification-based lab design was the sole focus. Evaluation surveys consisting of six questions were used at three different times to assess student knowledge of experimental concepts. In the general chemistry laboratory portion of this study, four experimental variants were employed to investigate the effect of relevance and lab design on student learning. These variants consisted of a traditional (or verification) lab design, a traditional lab design using "real world" samples, a new lab design employing real world samples/situations using unknown samples, and the new lab design using real world samples/situations that were known to the student. Data used in this analysis were collected during the Fall 08, Winter 09, and Fall 09 terms. For the second part of this study a cellulose regeneration experiment was employed to investigate the effects of lab design. A demonstration creating regenerated cellulose "rayon" was modified and converted to an efficient and low-waste experiment. In the first variant students tested their products and verified a list of physical properties. In the second variant, students filled in a blank physical property chart with their own experimental results for the physical properties. Results from the conductivity experiment show significant student learning of the effects of concentration on conductivity and how to use conductivity to differentiate solution types with the use of real world samples. In the organic chemistry experiment, results suggest that the discovery-based design improved student retention of the chain length differentiation by physical properties relative to the verification-based design.

Field programmable chemistry: integrated chemical and electronic processing of informational molecules towards electronic chemical cells.

PubMed

Wagler, Patrick F; Tangen, Uwe; Maeke, Thomas; McCaskill, John S

2012-07-01

The topic addressed is that of combining self-constructing chemical systems with electronic computation to form unconventional embedded computation systems performing complex nano-scale chemical tasks autonomously. The hybrid route to complex programmable chemistry, and ultimately to artificial cells based on novel chemistry, requires a solution of the two-way massively parallel coupling problem between digital electronics and chemical systems. We present a chemical microprocessor technology and show how it can provide a generic programmable platform for complex molecular processing tasks in Field Programmable Chemistry, including steps towards the grand challenge of constructing the first electronic chemical cells. Field programmable chemistry employs a massively parallel field of electrodes, under the control of latched voltages, which are used to modulate chemical activity. We implement such a field programmable chemistry which links to chemistry in rather generic, two-phase microfluidic channel networks that are separated into weakly coupled domains. Electric fields, produced by the high-density array of electrodes embedded in the channel floors, are used to control the transport of chemicals across the hydrodynamic barriers separating domains. In the absence of electric fields, separate microfluidic domains are essentially independent with only slow diffusional interchange of chemicals. Electronic chemical cells, based on chemical microprocessors, exploit a spatially resolved sandwich structure in which the electronic and chemical systems are locally coupled through homogeneous fine-grained actuation and sensor networks and play symmetric and complementary roles. We describe how these systems are fabricated, experimentally test their basic functionality, simulate their potential (e.g. for feed forward digital electrophoretic (FFDE) separation) and outline the application to building electronic chemical cells. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

Influence of Force Fields and Quantum Chemistry Approach on Spectral Densities of BChl a in Solution and in FMO Proteins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chandrasekaran, Suryanarayanan; Aghtar, Mortaza; Valleau, Stéphanie

2015-08-06

Studies on light-harvesting (LH) systems have attracted much attention after the finding of long-lived quantum coherences in the exciton dynamics of the Fenna–Matthews–Olson (FMO) complex. In this complex, excitation energy transfer occurs between the bacteriochlorophyll a (BChl a) pigments. Two quantum mechanics/molecular mechanics (QM/MM) studies, each with a different force-field and quantum chemistry approach, reported different excitation energy distributions for the FMO complex. To understand the reasons for these differences in the predicted excitation energies, we have carried out a comparative study between the simulations using the CHARMM and AMBER force field and the Zerner intermediate neglect of differential orbitalmore » (ZINDO)/S and time-dependent density functional theory (TDDFT) quantum chemistry methods. The calculations using the CHARMM force field together with ZINDO/S or TDDFT always show a wider spread in the energy distribution compared to those using the AMBER force field. High- or low-energy tails in these energy distributions result in larger values for the spectral density at low frequencies. A detailed study on individual BChl a molecules in solution shows that without the environment, the density of states is the same for both force field sets. Including the environmental point charges, however, the excitation energy distribution gets broader and, depending on the applied methods, also asymmetric. The excitation energy distribution predicted using TDDFT together with the AMBER force field shows a symmetric, Gaussian-like distribution.« less

Hydrological and solute budgets of Lake Qinghai, the largest lake on the Tibetan Plateau

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jin, Zhangdong; You, Chen-Feng; Wang, Yi

2009-12-04

Water level and chemistry of Lake Qinghai are sensitive to climate changes and are important for paleoclimatic implications. An accurate understanding of hydrological and chemical budgets is crucial for quantifying geochemical proxies and carbon cycle. Published results of water budget are firstly reviewed in this paper. Chemical budget and residence time of major dissolved constituents in the lake are estimated using reliable water budget and newly obtained data for seasonal water chemistry. The results indicate that carbonate weathering is the most important riverine process, resulting in dominance of Ca 2+ and DIC for river waters and groundwater. Groundwater contribution tomore » major dissolved constituents is relatively small (4.2 ± 0.5%). Wet atmospheric deposition contributes annually 7.4–44.0% soluble flux to the lake, resulting from eolian dust throughout the seasons. Estimates of chemical budget further suggest that (1) the Buha-type water dominates the chemical components of the lake water, (2) Na +, Cl -, Mg 2+ , and K + in lake water are enriched owing to their conservative behaviors, and (3) precipitation of authigenic carbonates (low-Mg calcite, aragonite, and dolomite) transits quickly dissolved Ca 2+ into the bottom sediments of the lake, resulting in very low Ca 2+ in the lake water. Therefore, authigenic carbonates in the sediments hold potential information on the relative contribution of different solute inputs to the lake and the lake chemistry in the past.« less

Quarterly progress report for the Chemical and Energy Research Section of the Chemical Technology Division: October-December 1997

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jubin, R.T.

This report summarizes the major activities conducted in the Chemical and Energy Research Section of the Chemical Technology Division at Oak Ridge National Laboratory (ORNL) during the period October--December 1997. The section conducts basic and applied research and development in chemical engineering, applied chemistry, and bioprocessing, with an emphasis on energy-driven technologies and advanced chemical separations for nuclear and waste applications. The report describes the various tasks performed within six major areas of research: Hot Cell Operations, Process Chemistry and Thermodynamics, Separations and Materials Synthesis, Fluid Structure and Properties, Biotechnology Research, and Molecular Studies. The name of a technical contactmore » is included with each task described, and readers are encouraged to contact these individuals if they need additional information. Activities conducted within the area of Hot Cell Operations included efforts to optimize the processing conditions for Enhanced Sludge Washing of Hanford tank sludge, the testing of candidate absorbers and ion exchangers under continuous-flow conditions using actual supernatant from the Melton Valley Storage Tanks, and attempts to develop a cesium-specific spherical inorganic sorbent for the treatment of acidic high-salt waste solutions. Within the area of Process Chemistry and Thermodynamics, the problem of solids formation in process solutions from caustic treatment of Hanford sludge was addressed and experimental collaborative efforts with Russian scientists to determine the solidification conditions of yttrium barium, and copper oxides from their melts were completed.« less

Transport of reacting solutes in porous media: Relation between mathematical nature of problem formulation and chemical nature of reactions

USGS Publications Warehouse

Rubin, Jacob

1983-01-01

Examples involving six broad reaction classes show that the nature of transport-affecting chemistry may have a profound effect on the mathematical character of solute transport problem formulation. Substantive mathematical diversity among such formulations is brought about principally by reaction properties that determine whether (1) the reaction can be regarded as being controlled by local chemical equilibria or whether it must be considered as being controlled by kinetics, (2) the reaction is homogeneous or heterogeneous, (3) the reaction is a surface reaction (adsorption, ion exchange) or one of the reactions of classical chemistry (e.g., precipitation, dissolution, oxidation, reduction, complex formation). These properties, as well as the choice of means to describe them, stipulate, for instance, (1) the type of chemical entities for which a formulation's basic, mass-balance equations should be written; (2) the nature of mathematical transformations needed to change the problem's basic equations into operational ones. These and other influences determine such mathematical features of problem formulations as the nature of the operational transport-equation system (e.g., whether it involves algebraic, partial-differential, or integro-partial-differential simultaneous equations), the type of nonlinearities of such a system, and the character of the boundaries (e.g., whether they are stationary or moving). Exploration of the reasons for the dependence of transport mathematics on transport chemistry suggests that many results of this dependence stem from the basic properties of the reactions' chemical-relation (i.e., equilibrium or rate) equations.

Three-Dimensional Printing Using a Photoinitiated Polymer

ERIC Educational Resources Information Center

Muskin, Joseph; Ragusa, Matthew; Gelsthorpe, Thomas

2010-01-01

Printers capable of producing three-dimensional objects are becoming more common. Most of these printers are impractical for use in the chemistry classroom because of the expense incurred in fabricating a print head that must be controlled in three dimensions. We propose a simpler solution to this problem that allows the emerging technology of…

Developing Laboratory Skills by Incorporating Peer-Review and Digital Badges

ERIC Educational Resources Information Center

Seery, Michael K.; Agustian, Hendra Y.; Doidge, Euan D.; Kucharski, Maciej M.; O'Connor, Helen M.; Price, Amy

2017-01-01

Laboratory work is at the core of any chemistry curriculum but literature on the assessment of laboratory skills is scant. In this study we report the use of a peer-observation protocol underpinned by exemplar videos. Students are required to watch exemplar videos for three techniques (titrations, distillations, preparation of standard solutions)…

Do-It-Yourself: 3D Models of Hydrogenic Orbitals through 3D Printing

ERIC Educational Resources Information Center

Griffith, Kaitlyn M.; de Cataldo, Riccardo; Fogarty, Keir H.

2016-01-01

Introductory chemistry students often have difficulty visualizing the 3-dimensional shapes of the hydrogenic electron orbitals without the aid of physical 3D models. Unfortunately, commercially available models can be quite expensive. 3D printing offers a solution for producing models of hydrogenic orbitals. 3D printing technology is widely…

Effects of Context on Students' Molecular-Level Ideas

ERIC Educational Resources Information Center

Teichert, Melonie A.; Tien, Lydia T.; Anthony, Seth; Rickey, Dawn

2008-01-01

In the studies reported here, we investigate the effects of context on students' molecular-level ideas regarding aqueous solutions. During one-on-one interviews, 19 general chemistry students recruited from a two-year community college and a research university in the United States were asked to describe their molecular-level ideas about various…

Science: Grade 8. Curriculum Bulletin 1967-68 Series No. 20. [Revised].

ERIC Educational Resources Information Center

New York City Board of Education, Brooklyn, NY. Div. of Curriculum and Instruction.

This document was developed to provide eighth-grade teachers in New York City with a sequence of instructional activities in science. The major portion of the guide is divided into four instructional units. The first unit, "Chemistry," includes lessons and activities on liquid solutions, suspensions and emulsions, acids, bases,…

"Gone" into Solution: Assessing the Effect of Hands-On Activity on Students' Comprehension of Solubility

ERIC Educational Resources Information Center

Bruck, Laura B.; Bruck, Aaron D.; Phelps, Amy J.

2010-01-01

Solubility is challenging for many general chemistry students, and the interactions of aqueous species are difficult to conceptualize. Derived from the pedagogies of Johnstone, Bloom, and Piaget, our primary research questions probe whether students' conceptual understandings of solubility could be enhanced by participation in a concept-building,…

Implementation of Aquaponics in Education: An Assessment of Challenges and Solutions

ERIC Educational Resources Information Center

Hart, Emily R.; Webb, James B.; Danylchuk, Andy J.

2013-01-01

Aquaponics is the combination of aquaculture and hydroponic technology to grow fish and plants together. While aquaponics can play a role in food security, it may also be a potential educational tool because of its interdisciplinary nature and required technological skills. With aquaponics, students could conduct activities involving chemistry,…

See the Light! A Nice Application of Calculus to Chemistry

ERIC Educational Resources Information Center

Boersma, Stuart; McGowan, Garrett

2007-01-01

Some simple modeling with Riemann sums can be used to develop Beer's Law, which describes the relationship between the absorbance of light and the concentration of the solution which the light is penetrating. A further application of the usefulness of Beer's Law in creating calibration curves is also presented. (Contains 3 figures.)

Role of solution chemistry in the retention and release of graphene oxide nanomaterials in uncoated and iron oxide-coated sand

EPA Science Inventory

Upon increasing production and use of graphene oxide nanoparticles (GONPs), concerns agitate over their potential impacts and risks to the environment, ecosystem, and human health. An improved understanding of the fate and transport including remobilization of GONPs in the subsur...

Introduction to Stochastic Simulations for Chemical and Physical Processes: Principles and Applications

ERIC Educational Resources Information Center

Weiss, Charles J.

2017-01-01

An introduction to digital stochastic simulations for modeling a variety of physical and chemical processes is presented. Despite the importance of stochastic simulations in chemistry, the prevalence of turn-key software solutions can impose a layer of abstraction between the user and the underlying approach obscuring the methodology being…

Using Texas Instruments Emulators as Teaching Tools in Quantitative Chemical Analysis

ERIC Educational Resources Information Center

Young, Vaneica Y.

2011-01-01

This technology report alerts upper-division undergraduate chemistry faculty and lecturers to the use of Texas Instruments emulators as virtual graphing calculators. These may be used in multimedia lectures to instruct students on the use of their graphing calculators to obtain solutions to complex chemical problems. (Contains 1 figure.)